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AN INTRODUCTION TO ENERGY SOURCES

NATIONAL CENTRE FOR CATALYSIS RESEARCH

DEPARTMENT OF CHEMISTRY
INDIAN INSTITUTE OF TECHNOLOGY, MADRAS

PREFACE

The reasons for the choice of energy sources are many. There is a need to know the
options available and how to exploit them, the need to harness some of these sources
efficiently and effectively and above all the environmental concerns these energy sources
give rise to. The material presented in the form of an e book is mainly meant for higher
secondary school students as the audience and for others this may be elementary unless
otherwise one wishes to get some basis on this topic.

Each of the chapters has been prepared by the individual members of the National Centre
for Catalysis Research keeping various factors in mind like the audience to whom the
subject matter is addressed to and the level of knowledge required to follow the contents
of the material. We do hope that this attempt has fulfilled all these expectations.
However, it should be remembered that there can be serious shortcomings in the
compilation. We do hope that the book in spite of these limitations may be useful to
some extent.

The material contained in this e book was the subject matter of a summer term course
delivered by the members of the National Centre for Catalysis Research to the
participants of the Chemistry programme organized by Childrens' Club of Madras.

This is one of our first attempts to bring out an e book and this effort will be improved in
the subsequent attempts only when appropriate feed back is given to us on various
aspects of this endeavour. We will be grateful for any feed back sent to us to our email
address bvnathan(S>iitm ac . in .

We do hope our ebook will receive considerable number of hits from the people who
seek to know about the possible energy sources.

Chennai 600 036

Dated 20 th October 2006 B.Viswanathan

Contents

S.No.

Chapter

Page No.

Energy sources

3-8

Petroleum

9-34

Natural Gas

35-49

Coal

50-84

Nuclear Fission

85-101

Nuclear Fusion

102-114

Introduction to Batteries

115-134

Solid State Batteries

135-152

Fuel Cells

153-175

Super capacitors

176-195

Photo-voltaic cells

196-210

Photo-electrochemical Cells

211-227

Hydrogen Production

228-243

Hydrogen Storage

244-263

Biochemical Energy Conversion Processes

264-287

Chapter -1

ENERGY SOURCES

B. Viswanathan

The standard of living of the people of any country is considered to be proportional to the
energy consumption by the people of that country. In one sense, the disparity one feels
from country to country arises from the extent of accessible energy for the citizens of
each country. Unfortunately, the world energy demands are mainly met by the fossil
fuels today. The geographical non equi-distribution of this source and also the ability to
acquire and also control the production and supply of this energy source have given rise
to many issues and also the disparity in the standard of living. To illustrate the points
that have been mentioned, it is necessary to analyze some data. In Table 1, the proved
reserves of some of the fossil fuels are given on the basis of regions.
Table 1 . Data on the proved reserves of fossil fuel on region-wise

Region/ OIL

Thousand
Million barrels
(1994)

Thousand
Million barrels
(2004)

R/P
Ratio

North America

89.8

11.8

South and Central America

81.5

101.2

40.9

Europe and Eurasia

80.3

139.2

21.6

So called Middle East

661.7

733.9

81.6

Africa

65.0

112.2

33.1

Asia pacific

39.2

41.1

14.2

Total world

1017.5

1188.6

40.5

Region/Natural gas

Trillion cubic
meters (1994)

Trillion cubic
meters (2004)

R/P ratio

North America

8.42

7.32

9.6

South and central America

5.83

7.10

55.0

Europe and Eurasia

63.87

64.02

60.9

So called Middle east

45.56

72.83

Africa

9.13

14.06

96.9

Energy sources

Asia pacific

10.07

14.21

43.9

World

142.89

179.53

66.7

Region/COAL

Million tones
(2004)

R/P ratio

North America

254432

235

South and central America

19893

290

Europe and Eurasia

287095

242

Africa and so called middle east

50755

204

Asia and pacific

296889

101

World

909064

164

The world energy consumption pattern is also increasing as shown in the Fig.l. The
energy consumption has been increasing and it will triple in a period of 50 years by 2025
as seen from Fig.l. Data on fossil fuel consumption by fuel type are given in Table 2.
The fossil fuel use as energy source has many limitations. There are a number of
pollutants that have been identified as coming out of the use of fossil fuels and they are
serious health hazards. A simple compilation of the type of effects of the pollutants from
fossil fuel sources is given in Table 3.

Fig.l. ENERGY CONSUMPTION 1970-

2025

~7ClCl

600

♦

400

■ann

.+.

„, -►* ♦

♦ Seriesl

Odd

♦ ♦

i dd

I960 1980 2000 2020 2040

YEARS

Fig. 1 . World energy consumption pattern

An Introduction to Energy Sources

Table 2. Energy consumption by fuel type (in million tones of oil equivalent) for the year
2004

Region

Oil

Gas

Coal

Nuclear
energy

Hydro-
electricity

Total

North America

1122.4

705.9

603.8

210.4

141.9

2784.4

South & central
America

221.7

106.2

18.7

4.4

132.1

483.1

Europe and Eurasia

957.3

997.7

537.2

287.2

184.7

2964.0

So called Middle east

250.9

218.0

9.1

4.0

481.9

Africa

124.3

61.8

102.8

3.4

19.8

312.1

Asia Pacific

1090.5

330.9

1506.6

118.9

152.0

3198.8

World

3767.1

242.4

2778.2

624.3

634.4

10224.4

The scene of energy resources have been visualized in terms of various parameters.
Mainly the population increase and also the need to increase the standard of living are the
factors forcing to see new and alternate energy options. The climate change which is
threatening the existence of life is another factor forcing to consider alternate energy
sources. However the energy sources to be adopted will have to meet the varying needs
of different countries and at the same time enhance the security of each one against the
energy crisis or energy shortage that have taken place in the past. The factors that need
consideration for the search for new energy sources should include:

(i) The global energy situation and demand

(ii) The availability of fossil sources

(iii) The efficiency of the energy sources

(iv) The availability of renewable sources

(v) The options for nuclear fission and fusion.

The world population will increase from 6 billion to 1 1 billion in this century and the life
expectancy has increased 2 times in the last two centuries and the energy requirement has
increased 35 times in the same period. The main drivers of the alternate energy search
are the population growth, economy, technology, and agriculture. This energy demand
will be in the non OECD countries and it is expected that in china alone the energy
demand will increase by 20% and this will shift the oil export from west to other non

6 Energy sources

OECD countries. Need for new and carbon free energy sources and possibly electricity
demand will go up in the coming years.

Energy from Nuclear fission though can be conceived as an alternate for the production
the necessary electrical energy, the current available technologies and reactors may not
be able to meet this demand. A global integrated system encompassing the complete fuel
cycle, water management, and fissile fuel breeding have to be evolved for this source of
energy to be a viable option.

The renewable energy sources are not brought into main stream energy resources though
occasionally we hear the use of low quality biomass as a source in some form or the
other. The carbon dioxide emission must be controlled in the vicinity of 600 to 650 ppm
in the period of 2030 to 2080. The exact slope of the curve is not a matter of concern the
cumulative amount of the carbon dioxide emission will be a factor to reckon with.
Therefore the alternative for energy supply should include fossil fuel with carbon dioxide
sequestration, nuclear energy and renewable energies. Possibly fusion and also
hydrogen based energy carrier system will evolve. However, the costs involved may
even force the shift to the use of coal as an energy source in countries like India and
China.

The adaptation of new energy sources also faces some limitations. One is not sure of the
feasibility and sustainability of such an energy source, and the learning curve also has
very limited gradient making investments restrictive.

Even though collaborative ventures between nations may be one option from the point of
view of investment, it is not certain whether any country will be willing to deploy giga
watts power not directly produced in the country of consumption. This is mainly due to
the experience from energy disruptions in the past and also the small elasticity of the
energy market. Countries will opt for a diversity of energy supply rather than depend on
a mega scale power plants since the possibility of alternate suppliers will be more
acceptable than the inter dependent supplies across countries, economy and
administration.

There are a variety of energy resources and energy forms. These include hydro power,
wind, solar, biomass and geothermal for resources and in the energy forms, light, heat,
electricity, hydrogen and fuel. How this transition has to occur depends on many factors

An Introduction to Energy Sources

but surely the transition has to take place sooner or later. What kind of mix will be
required also depends on the location and also the availability of the resources.
Photovoltaic devises have been advocated as a powerful energy source, but the
technology still needs high investment and also the reliability and sustainability questions
have to be addressed.
Table 3. Effect of pollutants on Human beings

Types

Effects

Primary pollutants

Heart disease, strokes, pneumonia, pulmonary tuberculosis,

congestion of brain and lungs.

so x

Acute respiratory infection ( chronic pulmonary or cardiac

disorders)

NO x

Chronic respiratory infection ( chromic bronchitis, emphysema

and pulmonary oedema)

Lung and stomach cancer

Tissue destruction of the respiratory epithelium ( deleterious

effects on the lining of the nose, sinus, throat and lungs) cancer

Pb and PbO x

Brain damage, cumulative poisoning (absorbed in red blood cells

and bone marrow.

Secondary pollutants

PANandN0 2

Attacks of acute asthma and allergic respiratory infections

(chronic bronchitis and emphysema).

Chest constriction, irritation of mucous membrane, headache,

coughing and exhaustion.

Aerosols

S0 4 2 "andN0 3 "

Asthma, infant mortality and acute respiratory infections

Others

Aldehydes, olefins,

Respiratory tract carcinoma

nitroamines PAH

Acrolein

Irritation to eyes

Chapter - 2
PETROLEUM

S. Chandravathanam

1. Introduction

Petroleum is oily, flammable, thick dark brown or greenish liquid that occurs naturally in
deposits, usually beneath the surface of the earth; it is also called as crude oil. Petroleum
means rock oil, (Petra - rock, elaion - oil, Greek and oleum - oil, Latin), the name
inherited for its discovery from the sedimentary rocks. It is used mostly for producing
fuel oil, which is the primary energy source today. Petroleum is also the raw material for
many chemical products, including solvents, fertilizers, pesticides and plastics. For its
high demand in our day-to-day life, it is also called as 'black gold'.
Oil in general has been used since early human history to keep fires ablaze, and also for
warfare. Its importance in the world economy evolved slowly. Wood and coal were used
to heat and cook, while whale oil was used for lighting. Whale oil however, produced a
black, smelly, thick liquid known as tar or rock oil and was seen as a substance to avoid.
When the whaling industry hunted the sperm whale almost to extinction and the
industrial revolution needed a fuel to run generators and engines, a new source of energy
was needed. In the search for new products, it was discovered that, from crude oil or
petroleum, kerosene could be extracted and used as a light and heating fuel. Petroleum
was in great demand by the end of the 1800's, forcing the creation of the petroleum
industry.

Petroleum is often considered the lifeblood of nearly all other industry. For its high
energy content (Table- 1) and ease of use, petroleum remains as the primary energy
source.

Table 1. Energy density of different fossil fuels

Fuel

Energy Density

Petroleum or Crude oil

45 MJ/Kg

Coal

24 MJ/Kg

Natural Gas

34-38 MJ/m 3

10 Petroleum

Oil accounts for 40% of the United States' energy supply and a comparable percentage of
the world's energy supply. The United States currently consumes 7.5 billion barrels (1.2
km 3 , 1 barrel =159 litre or 35 gallon) of oil per year, while the world at large consumes
30 billion barrels (4.8 km 3 ). Petroleum is unequally distributed throughout the world. The
United States, and most of the world, are net importers of the resource.
2. Origin of Petroleum

2.1. Biogenic theory

Most geologists view crude oil, like coal and natural gas, as the product of compression
and heating of ancient vegetation over geological time scales. According to this theory, it
is formed from the decayed remains of prehistoric marine animals and terrestrial plants.
Over many centuries this organic matter, mixed with mud, is buried under thick
sedimentary layers of material. The resulting high levels of heat and pressure cause the
remains to metamorphose, first into a waxy material known as kerogen, and then into
liquid and gaseous hydrocarbons in a process known as catagenesis. These then migrate
through adjacent rock layers until they become trapped underground in porous rocks
called reservoirs, forming an oil field, from which the liquid can be extracted by drilling
and pumping. 150 m is generally considered the "oil window". Though this corresponds
to different depths for different locations around the world, a 'typical' depth for an oil
window might be 4-5 km. Three situations must be present for oil reservoirs to form: a
rich source rock, a migration conduit, and a trap (seal) that forms the reservoir.
The reactions that produce oil and natural gas are often modeled as first order breakdown
reactions, where kerogen breaks down to oil and natural gas by another set of reactions.

2.2. Abiogenic theory

In 1866, Berthelot proposed that carbides are formed by the action of alkali metal on
carbonates. These carbides react with water to give rise to large quantities of acetylene,
which in turn is converted to petroleum at elevated temperatures and pressures. For
example, one can write the sequence as follows:

Alkali metal H 2 Temp, and pressure

CaC0 3 ► CaC 2 ► HC=CH ► Petroleum

Mendalejeff proposed another reaction sequence involving acetylene in the formation of
petroleum. He proposed that dilute acids or hot water react with the carbides of iron and

An Introduction to Energy Sources 1 1

manganese to produce a mixture of hydrocarbons from which petroleum could have
evolved. The reaction sequence according to the proposal of Mendelejeff is:

H + /H 2
FesC + Mn 3 C ► Hydrocarbons ► Petroleum

Iron Manganese

Carbide Carbide

These postulates based on inorganic chemicals, though interesting, cannot be completely
accepted for the following three reasons:

1 . One often finds optical activity in petroleum constituents which could not have been
present if the source of petroleum were only these inorganic chemicals.

2. Secondly, the presence of thermo-labile organic constituents (biomarkers) in petroleum
cannot be accounted for in terms of origin from these inorganic chemicals.

3. It is known that oil is exclusively found in sedimentary rocks, which would not have
been the case if the origin of oil could be attributed to processes involving only these
inorganic chemicals.

The theory is a minority opinion amongst geologists. This theory often pops us when
scientists are not able to explain apparent oil inflows into certain oil reservoirs. These
instances are rare.

In 1911, Engler proposed that an organic substance other than coal was the source
material of petroleum. He proposed the following three stages of development;

1. In the first stage, animal and vegetable deposits accumulate at the bottom of island seas
and are then decomposed by bacteria, the water soluble components are removed and
fats, waxes and other fat-soluble and stable materials remain.

2. In the second stage, high temperature and pressure cause carbon dioxide to be
produced from carboxyl-containing compounds, and water is produced from the hydroxyl
acids and alcohols to yield a bituminous residue. There can also be a little cracking,
producing a liquid product with a high olefin content (petropetroleum).

3. In the third stage, the unsaturated compounds are polymerized to naphthenic and/or
paraffinic hydrocarbons. Aromatics are presumed to be formed either by cracking and
cyclization or decomposition of petroleum . The elements of this theory has survived; the
only objection to it is that the end products obtained from the same sequence of

Petroleum

experiments namely, paraffins and unsaturated hydrocarbons differ from those of

petroleum.

3. Composition of Petroleum

Petroleum is a combination of gaseous, liquid and solid mixtures of many alkanes. It
consists principally of a mixture of hydrocarbons, with traces of various nitrogenous and
sulfurous compounds. Gaseous petroleum consists of lighter hydrocarbons with
abundant methane content and is termed as 'natural gas'. Liquid petroleum not only
consists of liquid hydrocarbons but also includes dissolved gases, waxes (solid
hydrocarbons) and bituminous material. Solid petroleum consists of heavier
hydrocarbons and this bituminous material is usually referred to as bitumen or asphalt.
Along with these, petroleum also contains smaller amounts of nickel, vanadium and other
elements.

Large deposits of petroleum have been found in widely different parts of the world and
their chemical composition varies greatly. Consequently the elemental composition of
petroleum vary greatly from crude oil to crude oil. It is not surprising that the
composition varies, since the local distribution of plant, animal and marine life is quite
varied and presumably was similarly varied when the petroleum precursors formed.
Furthermore, the geological history of each deposit is different and allows for varying
chemistry to have occurred as the organic matter originally deposited matured into
petroleum.
Table 2. Overall tank Composition of Petroleum

Element

Percentage composition

Carbon

83.0-87.0

Hydrogen

10.0-14.0

Nitrogen

0.1-2.0

Sulphur

0.05-6.0

Oxygen

0.05-1.5

Petroleum also contains trace levels of nickel and vanadium (« 1000 ppm).

An Introduction to Energy Sources 13

4. Production or Extraction of Petroleum

Locating an oil field is the first obstacle to be overcome. Today, petroleum engineers use
instruments such as gravimeters and magnetometers in the search for petroleum.
Generally, the first stage in the extraction of crude oil is to drill a well into the
underground reservoir. Often many wells (called multilateral wells) are drilled into the
same reservoir, to ensure that the extraction rate will be economically viable. Also, some
wells (secondary wells) may be used to pump water, steam, acids or various gas mixtures
into the reservoir to raise or maintain the reservoir pressure, and so maintain an economic
extraction rate.

4.1. Primary oil recovery

If the underground pressure in the oil reservoir is sufficient, then the oil will be forced to
the surface under this pressure. Gaseous fuels or natural gas are usually present, which
also supply needed underground pressure. In this situation, it is sufficient to place a
complex arrangement of valves on the well head to connect the well to a pipeline network
for storage and processing. This is called primary oil recovery. Usually, only about 20%
of the oil in a reservoir can be extracted this way.

4.2. Secondary oil recovery

Over the lifetime of the well, the pressure will fall, and at some point there will be
insufficient underground pressure to force the oil to the surface. If economical, and it
often is, the remaining oil in the well is extracted using secondary oil recovery methods.
Secondary oil recovery uses various techniques to aid in recovering oil from depleted or
low-pressure reservoirs. Sometimes pumps, such as beam pumps and electrical
submersible pumps are used to bring the oil to the surface. Other secondary recovery
techniques increase the reservoir's pressure by water injection, natural gas re-injection
and gas lift, which injects air, carbon dioxide or some other gas into the reservoir.
Together, primary and secondary recovery allow 25% to 35% of the reservoir's oil to be
recovered.

4.3 Tertiary oil recovery

Tertiary oil recovery reduces the oil's viscosity to increase oil production. Tertiary
recovery is started when secondary oil recovery techniques are no longer enough to
sustain production, but only when the oil can still be extracted profitably. This depends

14 Petroleum

on the cost of the extraction method and the current price of crude oil. When prices are
high, previously unprofitable wells are brought back into production and when they are
low, production is curtailed. Thermally enhanced oil recovery methods (TEOR) are
tertiary recovery techniques that heat the oil and make it easier to extract.

■ Steam injection is the most common form of TEOR, and is often done with a
cogeneration plant. In this type of cogeneration plant, a gas turbine is used to
generate electricity and the waste heat is used to produce steam, which is then
injected into the reservoir.

■ In-situ burning is another form of TEOR, but instead of steam, some of the oil is
burned to heat the surrounding oil.

■ Occasionally, detergents are also used to decrease oil viscosity.
Tertiary recovery allows another 5% to 15% of the reservoir's oil to be recovered.
5. Petroleum Refining

The petroleum industry can be divided into two broad groups: upstream producers
(exploration, development and production of crude oil or natural gas) and downstream
transporters (tanker, pipeline transport), refiners, retailers, and consumers.
Raw oil or unprocessed crude oil is not very useful in the form it comes in out of the
ground. It needs to be broken down into parts and refined before use in a solid material
such as plastics and foams, or as petroleum fossil fuels as in the case of automobile and
air plane engines. An oil refinery is an industrial process plant where crude oil is
processed in three ways in order to be useful petroleum products.
i) Separation - separates crude oil into various fractions

Oil can be used in so many various ways because it contains hydrocarbons of varying
molecular masses and lengths such as paraffins, aromatics, naphthenes (or cycloalkanes),
alkenes, dienes, and alkynes. Hydrocarbons are molecules of varying length and
complexity made of hydrogen and carbon. The trick in the separation of different
streams in oil refinement process is the difference in boiling points between the
hydrocarbons, which means they can be separated by distillation. Fig. 1 shows the
typical distillation scheme of an oil refinery.

An Introduction to Energy Sources

Crude oil

20°C
150°C

JTL_T£.

20Q°C

fr r- -r i t juj

; 300°0

i 370°C

rr?- T- TT> TT' :

Pefroleum
Gas

Gasolhe
(pelrd)

Kgrosene

Diesel

Industrial
luel oil

uutiricarting

oil, paraffin
wax aid
Asphalt

Fig. 1. Schematic of the distillation of crude oil

ii) Conversion - conversion to seleable products by skeletal alteration

Once separated and any contaminants and impurities have been removed, the oil can be
either sold with out any further processing, or smaller molecules such as isobutene and
propylene or butylenes can be recombined to meet specified octane number requirements
by processes such as alkylation or less commonly, dimerization. Octane number
requirement can also be improved by catalytic reforming, which strips hydrogen out of
hydrocarbons to produce aromatics, which have higher octane ratings. Intermediate
products such as gasoils can even be reprocessed to break a heavy, long-chained oil into
a lighter short-chained one, by various forms of cracking such as Fluid Catalytic
Cracking, Thermal Cracking, and Hydro-cracking. The final step in gasoline production

Petroleum

is the blending of fuels with different octane ratings, vapour pressures, and other

properties to meet product specification.

Table 2. Common Process Units in an Oil Refinery

Unit process

Function

Atmospheric Distillation Unit

Distills crude oil into fractions

Vacuum Distillation Unit

Further distills residual bottoms after
atmospheric distillation

Hydro -treat er Unit

desulfurizes naptha from atmospheric
distillation, before sending to a Catalytic
Reformer Unit

Catalytic Reformer Unit

reformate paraffins to aromatics, olefins,
and cyclic hydrocarbons, which are having
high octane number

Fluid Catalytic Cracking

break down heavier fractions into lighter,
more valuable products - by means of
catalytic system

Hydro-cracker Unit

break down heavier fractions into lighter,
more valuable products - by means of
steam

Alkylation Unit

produces high octane component by
increasing branching or alkylation

Dimerization Unit

smaller olefinic molecules of less octane
number are converted to molecules of
higher octane number by dimerization of
the smaller olefins

Isomerization Unit

straight chain normal alkanes of less octane
number are isomerized to branched chain
alkane of higher octane number

iii) Finishing - purification of the product streams
5.1. Details of Unit processes
5.1.1. Hydro-treater

A hydro-treater uses hydrogen to saturate aromatics and olefins as well as to remove
undesirable compounds of elements such as sulfur and nitrogen.

An Introduction to Energy Sources 17

Common major elements of a hydro-treater unit are a heater, a fixed-bed catalytic reactor
and a hydrogen compressor. The catalyst promotes the reaction of the hydrogen with the
sulfur compounds such as mercaptans to produce hydrogen sulfide, which is then usually
bled off and treated with amine in an amine treater. The hydrogen also saturated
hydrocarbon double bonds which helps raise the stability of the fuel.

5.1.2. Catalytic reforming

A catalytic reforming process converts a feed stream containing paraffins, olefins and
naphthenes into aromatics to be used either as a motor fuel blending stock, or as a source
for specific aromatic compounds, namely benzene, toluene and xylene for use in
petrochemicals production. The product stream of the reformer is generally referred to
as a reformate. Reformate produced by this process has a high octane rating. Significant
quantities of hydrogen are also produced as byproduct. Catalytic reforming is normally
facilitated by a bifunctional catalyst that is capable of rearranging and breaking long-
chain hydrocarbons as well as removing hydrogen from naphthenes to produce
aromatics. This process is different from steam reforming which is also a catalytic
process that produces hydrogen as the main product.

5.1.3. Cracking

In an oil refinery cracking processes allow the production of light products (such as LPG
and gasoline) from heavier crude oil distillation fractions (such as gas oils) and residues.
Fluid Catalytic Cracking (FCC) produces a high yield of gasoline and LPG while
Hydrocracking is a major source of jet fuel, gasoline components and LPG. Thermal
cracking is currently used to upgrade very heavy fractions or to produce light fractions or
distillates, burner fuel and/or petroleum coke. Two extremes of the thermal cracking in
terms of product range are represented by the high-temperature process called steam
cracking or pyro lysis (750-900 °C or more) which produces valuable ethylene and other
feedstocks for the petrochemical industry, and the milder-temperature delayed coking
(500 °C) which can produce, under the right conditions, valuable needle coke, a highly
crystalline petroleum coke used in the production of electrodes for the steel and
aluminum industries.

1 8 Petroleum

5.1.3.1. Fluid Catalytic Cracking

Initial process implementations were based on a low activity alumina catalyst and a
reactor where the catalyst particles were suspended in rising flow of feed hydrocarbons
in a fluidized bed. In newer designs, cracking takes place using a very active zeolite-
based catalyst in a short-contact time vertical or upward sloped pipe called the "riser".
Pre-heated feed is sprayed into the base of the riser via feed nozzles where it contacts
extremely hot fluidized catalyst at 665 to 760 °C. The hot catalyst vaporizes the feed and
catalyzed the cracking reactions that break down the high molecular weight oil into
lighter components including LPG, gasoline, and diesel. The catalyst-hydrocarbon
mixture flows upward through the riser for just a few seconds and then the mixture is
separated via cyclones. The catalyst-free hydrocarbons are routed to a main fractionator
for separation into fuel gas, LPG, gasoline, light cycle oils used in diesel and jet fuel, and
heavy fuel oil.

The catalytic cracking process involves the presence of acid catalysts (usually solid acids
such as silica-alumina and zeolites) which promote a heterolytic (asymmetric) breakage
of bonds yielding pairs of ions of opposite charges, usually a carbocation and the very
unstable hydride anion.

During the trip up the riser, the cracking catalyst is "spent" by reactions which deposit
coke on the catalyst and greatly reduce activity and selectivity. The "spent" catalyst is
disengaged from the cracked hydrocarbon vapours and sent to a stripper where it is
contacted with steam to remove hydrocarbons remaining in the catalyst pores. The
"spent" catalyst then flows into a fluidized-bed regenerator where air (or in some cases
air and oxygen) is used to burn off the coke to restore catalyst and also provide the
necessary heat for the next reaction cycle, cracking being an endothermic reaction. The
"regenerated" catalyst then flows to the base of the riser, repeating the cycle.

5.1.3.2. Hydrocracking

Hydrocracking is a catalytic cracking process assisted by the presence of an elevated
partial pressure of hydrogen. The products of this process are saturated hydrocarbons;
depending on the reaction conditions (temperature, pressure, catalyst activity) these
products range from ethane, LPG to heavier hydrocarbons comprising mostly of
isopraffins. Hydrocracking is normally facilitated by a bifunctional catalyst that is

An Introduction to Energy Sources 19

capable of rearranging and breaking hydrocarbon chains as well as adding hydrogen to
aromatics and olefins to produce naphthenes and alkanes. Major products from
hydrocracking are jet fuel, diesel, relatively high octane rating gasoline fractions and
LPG. All these products have a very low content of sulfur and contaminants.
5.1.3.3. Steam Cracking

Steam cracking is a petrochemical process in which saturated hydrocarbons are broken
down into smaller, often unsaturated, hydrocarbons. It is the principal industrial method
for producing the lighter alkenes (commonly olefins), including ethane (ethylene) and
propene (propylene).

In steam cracking, a gaseous or liquid hydrocarbon feed like naphtha, LPG or ethane is
diluted with steam and then briefly heated in a furnace (obviously with out the presence
of oxygen). Typically, the reaction temperature is very hot; around 850 °C, but the
reaction is only allowed to take place very briefly. In modern cracking furnaces, the
residence time is even reduced to milliseconds (resulting in gas velocities reaching
speeds beyond the speed of sound) in order to improve the yield of desired products.
After the cracking temperature has been reached, the gas is quickly quenched to stop the
reaction in a transfer line exchanger.

The products produced in the reaction depend on the composition of the feed, the
hydrocarbon to steam ratio and on the cracking temperature and furnace residence time.
Light hydrocarbon feeds (such as ethane, LPGs or light naphthas) give product streams
rich in the lighter alkenes, including ethylene, propylene, and butadiene. Heavier
hydrocarbon (full range and heavy naphthas as well as other refinery products) feeds
give some of these, but also give products rich in aromatic hydrocarbons and
hydrocarbons suitable for inclusion in gasoline or fuel oil. The higher cracking
temperature (also referred to as severity) favours the production of ethane and benzene,
where as lower severity produces relatively higher amounts of propene, C4-
hydrocarbons and liquid products.

The thermal cracking process follows a hemolytic mechanism, that is, bonds break
symmetrically and thus pairs of free radicals are formed. The main reactions that take
place include:

20 Petroleum

Initiation reactions, where a single molecule breaks apart into two free radicals. Only a
small fraction of the feed molecules actually undergo initiation, but these reactions are
necessary to produce the free radicals that drive the rest of the reactions. In steam
cracking, initiation usually involves breaking a chemical bond between two carbon
atoms, rather than the bond between a carbon and a hydrogen atom.

CH3CH3 ► 2CH 3 *

Hydrogen abstraction, where a free radical removes a hydrogen atom from another
molecule, turning the second molecule into a free radical.

CH 3 * + CH3CH3 ►CH 4 + CH 3 CH 2 *

Radical decomposition, where a free radical breaks apart into two molecules, one an
alkene, the other a free radical. This is the process that results in the alkene products of
steam cracking.

CH3CH2* ► CH 2 =CH 2 + H*

Radical addition, the reverse of radical decomposition, in which a radical reacts with an
alkene to form a single, larger free radical. These processes are involved in forming the
aromatic products that result when heavier feedstocks are used.

CH 3 CH 2 *+CH 2 =CH 2 ► CH3CH 2 CH 2 CH 2 *

Termination reactions, which happen when two free radicals react with each other to
produce products that are not free radicals. Two common forms of termination are
recombination, where the two radicals combine to form one larger molecule, and
disproportionation, where one radical transfers a hydrogen atom to the other, giving an
alkene and an alkane.

CH 3 * + CH 3 CH 2 * ► CH 3 CH 2 CH 3

CH 3 CH 2 * + CH 3 CH 2 * ► CH 2 =CH 2 + CH3CH3

The process also results in the slow deposition of coke, a form of carbon, on the reactor

walls. This degrades the effectiveness of the reactor, so reaction conditions are designed

to minimize this. Nonetheless, a steam cracking furnace can usually only run for a few

months at a time between de-cokings.

5.1.4. Alkylation

Alkylation is the transfer of an alkyl group from one molecule to another. The alkyl

group may be transferred as a alkyl carbocation, a free radical or a carbanion.

An Introduction to Energy Sources 21

In a standard oil refinery process, alkylation involves low-molecular-weight olefins
(primarily a mixture of propylene and butylenes) with isobutene in the presence of a
catalyst, either sulfuric acid or hydrofluoric acid. The product is called alkylate and is
composed of a mixture of high-octane, branched-chain paraffin hydrocarbons. Alkylate
is a premium gasoline blending stock because it has exceptional antiknock properties and
is clean burning.

Most crude oils contain only 10 to 40 percent of their hydrocarbon constituents in the
gasoline range, so refineries use cracking processes, which convert high molecular
weight hydrocarbons into smaller and more volatile compounds. Polymeriation converts
small gaseous olefins into liquid gasoline-size hydrocarbons. Alkylation processes
transform small olefin and iso-paraffin molecules into larger iso-paraffins with a high
octane number. Combining cracking, polymerization, and alkylation can result in a
gasoline yield representing 70 percent of the starting crude oil.
5.1.5. Isomerization

Isomerization is a process by which straight chain alkanes are converted to branched
chain alkanes that can be blended in petrol to improve its octane rating (in presence of
finely dispersed platinum on aluminium oxide catalyst).
6. Products of oil refinery
6.1. Asphalt

The term asphalt is often used as an abbreviation for asphalt concrete. Asphalt is a
sticky, black and highly viscous liquid or semi-solid that is present in most crude
petroleum and in some natural deposits. Asphalt is composed almost entirely of
bitument. Asphalt is sometimes confused with tar, which is an artificial material
produced by the destructive distillation or organic matter. Tar is also predominantly
composed of bitumen; however the bitumen content of tar is typically lower than that of
asphalt. Tar and asphalt have different engineering properties.

Asphalt can be separated from the other components in crude oil (such as naphtha,
gasoline and diesel) by the process of fractional distillation, usually under vacuum
conditions. A better separation can be achieved by further processing of the heavier
fraction of the crude oil in a de-asphalting unit which uses either propane or butane in a
processing is possible by "blowing" the product: namely reacting it with oxygen. This

22 Petroleum

makes the product harder and more viscous. Asphalt is rather hard to transport in bulk
(it hardens unless kept very hot). So it is sometimes mixed with diesel oil or kerosene
before shipping. Upon delivery, these lighter materials are separated out of the mixture.
This mixture is often called bitumen feedstock, or BFS.

The largest use of asphalt is for making asphalt concrete for pavements. Roofing
shingles account for most of the remaining asphalt consumption. Other uses include
cattle sprays, fence post treatments, and waterproofing for fabrics. The ancient middle-
east natural asphalt deposits were used for mortar between bricks and stones, ship caulk,
and waterproofing.
6.2. Diesel Fuel

Petroleum derived diesel is composed of about 75% saturated hydrocarbons (primarily
paraffins including n, iso, and cycloparaffins), and 25% aromatic hydrocarbons
(including naphthalens and alkylbenzenes). The average chemical formula for common
diesel fuel is C12H26, ranging from approximately, C10H22 to C15H32.
Diesel is produced from petroleum, and is sometimes called petrodiesel when there is a
need to distinguish it from diesel obtained from other sources. As a hydrocarbon
mixture, it is obtained in the fractional distillation of crude oil between 250 °C and 350
°C at atmospheric pressure.

petro-diesel is considered to be a fuel oil and is about 18% denser than gasoline. The
density of diesel is about 850 grams per liter whereas gasoline has a density of about 720
g/1, or about 18% less. Diesel is generally simpler to refine than gasoline and often costs
less.

Diesel fuel, however, often contains higher quantities of sulfur. High levels of sulfur in
diesel are harmful for the environment. It prevents the use of catalytic diesel particulate
filters to control diesel particulate emissions, as well as more advanced technologies
such as nitrogen oxide (NOx) absorbers, to reduce emission. However, lowering sulfur
also reduces the lubricity of the fuel, meaning that additives must be put into the fuel to
help lubricate engines. Biodiesel is an effective lubricant. Diesel contains
approximately 18% more energy per unit of volume than gasoline, which, along with the
greater efficiency of diesel engines, contributes to fuel economy.

An Introduction to Energy Sources 23

Synthetic diesel

Wood, straw, corn, garbage, and sewage-slude may be dried and gasified. After
purification, Fischer Tropsch process is used to produce synthetic diesel. Other attempts
use enzymatic processes and are also economic in case of high oil prices.
Biodiesel

Biodiesel can be obtained from vegetable oil and animal fats (bio-lipids, using trans-
esterification). Biodiesel is a non-fossil fuel alternative to petrodiesel. There have been
reports that a diesel-biodiesel mix results in lower emissions that either can achieve
alone. A small percentage of biodiesel can be used as an additive in low-sulfur
formulations of diesel to increase the lubricity lost when the sulfur is removed.
Chemically, most biodiesel consists of alkyl (usually methyl) esters instead of the
alkanes and aromatic hydrocarbons of petroleum derived diesel. However, biodiesel has
combustion properties very similar to petrodiesel, including combustion energy and
cetane ratings. Paraffin biodiesel also exists. Due to the purity of the source, it has a
higher quality than petrodiesel.

6.3. Fuel Oil

Fuel oil is a fraction obtained from petroleum distillation, either as a distillate or a
residue. Broadly speaking, fuel oil is any liquid petroleum product that is burned in a
furnace for the generation of heat or used in an engine for the generation of power. Fuel
oil is made of long hydrocarbon chains, particularly alkanes, cycloalkanes and aromatics.
Factually and in a stricter sense, the term fuel oil is used to indicate the heaviest
commercial fuel that can be obtained from crude oil, heavier than gasoline and naphtha.
Fuel oil is classified into six classes, according to its boiling temperature, composition
and purpose. The boiling point ranges from 175 to 600 C, and carbon chain length, 20 to
70 atoms. These are mainly used in ships with varying blending proportions.

6.4. Gasoline

Gasoline (or petrol) is a petroleum-derived liquid mixture consisting primarily of
hydrocarbons, used as fuel in internal combustion engines. Gasoline is separated from
crude oil via distillation, called natural gasoline, will not meet the required specifications
for modern engines (in particular octane rating), but these streams will form of the blend.

24 Petroleum

The bulk of a typical gasoline consists of hydrocarbons between 5 to 12 carbon atoms
per molecule.

The various refinery streams produce gasoline of different characteristics. Some
important streams are:

■ Reformate, produced in a catalytic reformer with a high octane and high
aromatics content, and very low olefins (alkenes).

■ Catalytically Cracked Gasoline or Catalytically Cracked Naphtha, produced from
a catalytic cracker, with a moderate octane, high olefins (alkene) content, and
moderate aromatics level.

■ Product from a hydrocracker, contains medium to low octane and moderate
aromatic levels.

■ Natural Gasoline, directly from crude oil contains low octane, low aromatics
(depending on the crude oil), some naphthenes (cycloalkanes) and zero olefins
(alkenes).

■ Alkylate, produced in an alkylation unit, with a high octane and which is pure
paraffin (alkane), mainly branched chains.

■ Isomerate, which is made by isomerising natural gasoline to increase its octane
rating and is very low in aromatics and benzene content.

Overall a typical gasoline is predominantly a mixture of paraffins (alkanes), naphthenes
(cycloalkanes), aromatics and olefins (alkenes). The exact ratios can depend on

■ The oil refinery that makes the gasoline, as not all refineries have the same set of
processing units.

■ The crude oil used by the refinery on a particular day.

■ The grade of gasoline, in particular the octane.
6.4.1. Octane rating

Octane number is a figure of merit representing the resistance of gasoline to premature
detonation when exposed to heat and pressure in the combustion chamber of an internal
combustion engine. Such detonation is wasteful of the energy in the fuel and potentially
damaging to the engine; premature detonation is indicated by knocking or ringing noises
that occur as the engine operates. If an engine running on a particular gasoline makes
such noises, they can be lessened or eliminated by using a gasoline with a higher octane

An Introduction to Energy Sources 25

number. The octane number of a sample of fuel is determined by burning the gasoline in
an engine under controlled conditions, e.g., of spark timing, compression, engine speed,
and load, until a standard level of knock occurs. The engine is next operated on a fuel
blended from a form of isooctane (octane number 100) that is very resistant to knocking
and a form of heptane (octane number 0) that knocks very easily. When a blend is found
that duplicates the knocking intensity of the sample under test, the percentage of
isooctane by volume in the blended sample is taken as the octane number of the fuel.
Octane numbers higher than 100 are determined by measuring the amount of tetraethyl
lead that must be added to pure isooctane so as to duplicate the knocking of a sample
fuel. Factors which can increase the octane number are more branching: 2-methylbutane
is less likely to autoignite than pentane. Shorter chains: pentane is less likely to
autoignite than heptane.

6.4.2. Additives to gasoline for value addition

Additives have been added to increase the value addition of gasoline either octane
number or combustion capacity.

6.4.2.1. To increase octane number

The discovery that lead additives reduced the knocking property of gasoline in internal
combustion engine led to the widespread adoption of the practice in the 1920s and
therefore more powerful higher compression engines. The most popular additive was
tetra-ethyl lead. However, with the recognition of the environmental damage caused by
lead, and the incompatibility of lead with catalytic converters found on virtually all
automobiles since 1975, this practice began to wane in the 1980s. Most countries are
phasing out leaded fuel; different additives have replaced the lead compounds. The most
popular additives include aromatic hydrocarbons, ethers and alcohol (usually ethanol
or methanol).

6.4.2.2. To increase combustion capacity

Oxygenate blending increases oxygen to the fuel in oxygen-bearing compounds such as
MTBE, ethanol and ETBE, and so reduces the amount of carbon monoxide and
unburned fuel in the exhaust gas, thus reducing smog. MTBE use is being phased out in
some countries due to issues with contamination of ground water. Ethanol and to a
lesser extent the ethanol derived ETBE are a common replacements. Especially ethanol

Petroleum

derived from bio-matter such as corn, sugar cane or grain is frequent, this will often be
referred to as bio-ethanol. An ethanol-gasoline mix of 10% ethanol mixed with gasoline
is called gasohol.
6.4.3. Energy content

Gasoline contains about 45 mega joules per kilogram (MJ/kg) or 135 MJ/US gallon. A
high octane fuel such as LPG has lower energy content than lower octane gasoline,
resulting in an overall lower power output at the regular compression ratio of an engine
that runs on gasoline. However, with an engine tuned to the use of LPG (i.e., via higher
compression ratios such as 12:1 instead of 8:1), this lower power output can be
overcome. This is because higher - Octane fuels allow for higher compression ratio.
Volumetric energy density of some fuels compared to gasoline is given in Table 4.
Table 4. Energy content of different fuels obtained from petroleum

Fuel type

MJ/L

MJ/kg

Gasoline

29.0

LPG

22.16

34.39

Ethanol

19.59

30.40

Methanol

14.57

22.61

Gasohol (10% ethanol + 90 % gasoline)

28.06

43.54

Diesel

40.9

63.47

6.5. Kerosene

Kerosene is a colourless flammable hydrocarbon liquid. Kerosene is obtained from the
fractional distillation of petroleum at 150 C and 275 C (carbon chains from C12 to C15
range). Typically, kerosene directly distilled from crude oil requires some treatment in
an hydro-treater, to reduce its sulfur content.

At one time it was widely used in kerosene lamps but it is now mainly used in aviation
fuel for jet engines. A form of kerosene known as RP-1 is burnt with liquid oxygen as
rocket fuel. Its use as a cooking fuel is mostly restricted to some portable stoves in less
developed countries, where it is usually less refined and contains impurities and even
debris. It can also be used to remove lice from hair, but stings and can be dangerous on

An Introduction to Energy Sources 27

skin. Most of these uses of kerosene created thick black smoke because of the low
temperature of combustion. It is also used as an organic solvent.

6.6. Liquefied petroleum gas

LPG is manufactured during the refining of crude oil, or extracted from oil or gas
streams as they emerge from the ground. Liquefied petroleum gas (also called liquefied
petroleum gas, liquid petroleum gas, LPG, LP Gas, or auto gas) is a mixture of
hydrocarbon gases used as a fuel in cooking, heating appliances, vehicles, and
increasingly replacing fluorocarbons as an aerosol propellant and a refrigerant to reduce
damage to the ozone layer. Varieties of LPG bought and sold include mixes that are
primarily propane, mixes that are primarily butane, and mixes including both propane
and butane, depending on the season. Propylene and butylenes are usually also present
in small concentrations. A powerful odorant, ethanethiol, is added so that leaks can be
detected easily.

At normal temperatures and pressures, LPG will evaporate. Because of this, LPG is
supplied in pressurized steel bottles. In order to allow for thermal expansion of the
contained liquid, these bottles should not be filled completely; typically, they are filled to
between 80% and 85% of their capacity.

6.7. Lubricant

A lubricant is introduced between two moving surfaces to reduce the friction and wear

between them. A lubricant provides a protective film which allows for two touching

surfaces to be separated, thus lessening the friction between them.

Typically lubricants contain 90% base oil (most often petroleum fractions, called mineral

oils) and less than 10% additives. Vegetable oils or synthetic liquids such as

hydrogenated polyolefins, esters, silicone, fluorocarbons and many others are sometimes

used as base oils. Additives deliver reduced friction and wear, increased viscosity,

resistance to corrosion and oxidation, aging or contamination.

In developed nations, lubricants contribute to nearly % of total pollution released to

environment. Spent lubricants are referred to as used oil or waste oil. As a liquid waste,

one liter of used oil can contaminate one million liters of water.

28 Petroleum

6.8. Paraffin

Paraffin is a common name for a group of high molecular weight alkane hydrocarbons
with the general formula C n H2 n +2, where n is greater than about 20. It is also called as
paraffin wax. Paraffin is also a technical name for an alkane in general, but in most cases
it refers specifically to a linear, or normal alkane, while branched, or isoalkanes are also
called isoparaffins.

It is mostly found as a white, odourless, tasteless, waxy solid, with a typical melting
point between about 47 °C to 65 °C. It is insoluble in water, but soluble in ether,
benzene, and certain esters. Paraffin is unaffected by most common chemical reagents,
but burns readily.

Liquid paraffin has a number of names, including nujol, mineral spirits, adepsine oil,
alboline, glymol, liquid paraffin oil, saxol, or USP mineral oil. It is often used in
infrared spectroscopy, as it has a relatively uncomplicated IR spectrum.
Paraffin is used in

■ Candle making

■ Coatings for waxed paper or cloth

■ Coatings for many kinds of hard cheese

■ As anticaking, moisture repellent and dust binding coatings for fertilizers

■ Preparing specimens for histology

■ Solid propellant for hybrid rockets

■ Sealing jars, cans, and bottles

■ In dermatology, as an emollient (moisturizer)

■ Surfing, for grip on surfboards as a component of surfwax

■ The primary component of glide wax, used on skis and snowboards

■ As a food additive

■ Used in forensics to detect granules of gunpowder in the hand of a shooting
suspect

■ Food-grade paraffin wax is used in some candies to make them look shiny

■ Impure mixtures of mostly paraffin wax are used in wax baths for beauty and
therapy purposes

An Introduction to Energy Sources 29

6.9. Mineral Oil

Mineral oil is a by-product in the distillation of petroleum to produce gasoline. It is
chemically-inert transparent colourless oil composed mainly of alkanes and cyclic
paraffins, related to white petroleum. Mineral oil is a substance of relatively low value,
and is produced in a very large quantities. Mineral oil is available in light and heavy
grades, and can often be found in drug stores. It is used in the following:

Refined mineral oil is used as transformer oil

Mineral oil is used to store and transport alkali metals. The oil prevents the

metals from reacting with atmospheric moisture.

Personal care

Mineral oil is sometimes taken orally as a laxative. It works by lubricating feces

and the intestinal mucus membranes

Mineral oil with added fragrance is marketed as 'baby oil' in the US and UK

Used as an ingredient in baby lotions, cold creams, ointments and other

pharmaceuticals and cosmetics

Can also be used for eyelashes; can generally be used to prevent brittleness and/or

breaking of lashes

Lubrication

Coolant

Low viscosity mineral oil is old as a preservative for wooden cutting boards and

utensils

A coating of mineral oil is excellent at protecting metal surfaces from moisture

and oxidation

Food-preparation butcher block surfaces are often conditioned periodically with

mineral oil

Light mineral oil is used in textile industries and used as a jute batching oil

Mineral oil is used as a sealer for soapstone countertops

Sometimes used in the food industry (particularly for candies)

Used as a cleaner and solvent for inks in fine art printmaking

30 Petroleum

6.10. Tar

Tar is viscous black liquid derived from the destructive distillation of organic matter.

Most tar is produced from coal as a byproduct of coke production, but it can also be

produced from petroleum, peat or wood. The use of the word "tar" is frequently a

misnomer. Naturally occurring "tar pits" actually contain asphalt, not tar, and are more

accurately called as asphalt pits. Tar sand deposits contain bitumen rather than tar.

Tar, of which surprisingly petroleum tar is the most effective, is used in treatment of

psoriasis. Tar is a disinfectant substance, and is used as such. Petroleum tar was also

used in ancient Egyptian mummification circa 1000 BC.

Tar was a vital component of the first sealed, or "tarmac", roads. It was also used as seal

for roofing shingles and to seal the hulls of ships and boats. It was also used to

waterproof sails, but today sails made from naturally waterproof synthetic substances

have negated the need for sail sealing.

Wood tar is still used to seal traditional wooden boats and the roofs of historical shingle

roofed churches. Wood tar is also available diluted as tar water, which has numerous

uses:

■ Flavoring for candies and alcohol

■ Scent for saunas

■ Anti-dandruff agent in shampoo

■ As a component of cosmetics

6.11. Bitumen

Bitumen is a category of organic liquids that are highly viscous, black, sticky and wholly
soluble in carbon disulfide. Asphalt and tar are the most common forms of bitumen.
Bitumen in the form of asphalt is obtained by fractional distillation of crude oil. Bitumen
being the heaviest and being the fraction with the highest boiling point, it appears as the
bottommost fraction. Bitumen in the form of tar is obtained by the destructive distillation
of organic matter, usually bituminous coal.

Bitumen is primarily used for paving roads. It is also the prime feed stock for petroleum
production from tar sands currently under development in Alberta, Canada. In the past,
bitumen was used to waterproof boats, and even as a coating for buildings, for example,

An Introduction to Energy Sources 3 1

that the city of Carthage was easily burnt down due to extensive use of bitumen in

construction.

Most geologists believe that naturally occurring deposits of bitumen are formed from the

remains of ancient, microscopic algae and other once-living things. These organisms

died and their remains were deposited I the mud on the bottom of the ocean or lake where

they lived. Under the hat and pressure of burial deep in the earth, the remains were

transformed into materials such a bitumen, kerogen, or petroleum. A minority of

geologists, proponents of the theory of abiogenic petroleum origin, believe that bitumen

and other hydrocarbons heavier than methane originally derive from deep inside the

mangle of the earth rather than biological detritus.

6.12. Pitch (resin)

Pitch is the name for any of a number of highly viscous liquids which appear solid. Pitch

can be made from petroleum products or plants. Petroleum-derived pitch is also called

bitumen. Pitch produced from plants is also known as resin or rosin.

Tar pitch appears solid, and can be shattered with a hard impact, but it is actually a liquid.

Pitch flows at room temperature, but extremely slowly. Pitch has a viscosity

approximately 100 billion (10 11 ) times that of water.

Pitch was traditionally used to help caulk the seams of wooden sailing vessels. It was

heated, put into a container with a very long spout. The word pitcher is said to derive

from this long spouted container used to pour hot pitch.

7. Petrochemicals

According to crude oil composition and demand, refineries can produce different shares

of petroleum products. Largest share of oil products is used as energy carriers: various

grades of fuel oil and gasoline. Refineries also produce other chemicals, some of which

are used in chemical processes to produce plastics and other useful materials. Since

petroleum often contains a couple of percent sulfur, large quantities are sulfur is also

often produced as a petroleum product. Carbon and hydrogen may also be produced as

petroleum products. The hydrogen produced is often used as an intermediate product for

other oil refinery processes such as hydrocracking and hydrodesulfurization.

A petrochemical is any chemical derived from fossil fuels. These include purified fossil

fuels such as methane, propane, butane, gasoline, kerosene, diesel fuel, aviation fuel, or

Petroleum

fuel oil and also include many agricultural chemicals such as pesticides, herbicides and
fertilizers, and other items such as plastics, asphalt and synthetic fibers. Also a wide
variety of industrial chemicals are petrochemicals. As petroleum products are feed stocks
for many industries, frequently chemical plants are sited adjacent to a refinery, utilizing
intermediate products of the refinery as feed stocks for the production of specialized
materials such as plastics or agrochemicals.
Table 5. Partial list of major commercial petrochemicals derived from petroleum sources

Ethylene

Poly ethylene

Ethylene oxide

Ethylene glycols

Poly esters
Engine coolant

Glycol esters

ethoxylates

Vinyl acetate

1 ,2 Dichloroethane

Trichloroethylene

Tetrachloroethylene

Vinyl chloride

Polyvinyl chloride

Ethyl benzene

styrene

Poly styrene

Synthetic rubbers

Higher olefins

Detergent alcohols

Propylene

cumene

Acetone

Bisphenol A

Epoxy resins

Poly carbonate

Solvents

Isopropyl alcohol

Acrylonitrile

Polypropylene

Propylene oxide

Propylene glycol

Glycol esters

Acrylic acid

Allyl chloride

Epichlorohydrin

Epoxyresins

An Introduction to Energy Sources

Butadiene

Synthetic rubbers

Benzene

Ethyl benzene

Styrene

Polystyrene

Synthetic rubber

Cumene

Phenol

Bisphenol A

Epoxy resins

Polycarbonate

cyclohexane

Adipic acid

Nylons

caprolactam

Nylons

Nitrobenzene

aniline

Methylene diphenyl
Diisocyanate (MDI)

Poly urethanes

Alkyl benzene

Detergents

Chlorobenzene

Toluene

Benzene

Toluene isocyanate

Polyurethanes

Benzoic acid

caprolactam

Nylon

Mixed xylenes

Ortho xylene

Phthalic anhydride

Para xylene

Dimethyl terethalate

Poly esters

Purified terephthalic
acid

Poly esters

8. Remarks

As has been seen, petroleum serves as an extensive source for the energy need as well as
feed stock for the spectrum of industries. Petroleum is a non-renewable natural resource
and the industry is faced with the inevitable eventual depletion of the world's oil supply.
By the very definition of non-renewable resources, oil exploration alone will not save off
future shortages of the resource. Resource economists argue that oil prices will rise as
demand increases relative to supply, and that this will spur further exploration and
development. However, this process will not increase the amount of oil in the ground, but
will rather temporarily prolong production as higher prices make it economical to extent
oil that was previously not economically recoverable.

34 Petroleum

References

1. R. Narayan and B. Viswanathan, 'Chemical and Electrochemical Energy Systems',
University Press, 1998.

2. http://en.wikipedia.org/wiki/Petro

Chapter - 3
NATURAL GAS

V. Chidambaram

1. Introduction

Natural gas has emerged as promising fuel due to its environment friendly nature,
efficiency, and cost effectiveness. Natural gas is considered to be most eco-friendly
fuel based on available information. Economically natural gas is more efficient since
only 10 % of the produced gas wasted before consumption and it does not need to be
generated from other fuels. Moreover natural gas is used in its normal state. Natural
gas has high heat content of about 1000 to 11000 Btu per Scf for pipeline quality gas
and it has high flame temperature. Natural gas is easy to handle and convenient to use
and energy equivalent basis, it has been price controlled below its competitor oil. It is
also suitable chemical feedstock for petrochemical industry. Hence natural gas can
substitute oil in both sectors namely fuels (industry and domestic) and chemicals
(fertilizer petrochemicals and organic chemicals).

2. Natural gas occurrence and production

Natural gas was formed from the remains of tiny sea animals and plants that died
200-400 million years ago. The ancient people of Greece, Persia, and India
discovered natural gas many centuries ago.
Table 1 . Time line for natural gas history in recent times

Year

Natural gas usage

1816

First used in America to illuminate Baltimore

1821

William Hart dug the first successful American natural gas well in
Fredonia, New York

1858

Fredonia Gas Light Company opened its doors in 1858 as the nation's
first natural gas company

1900

natural gas had been discovered in 17 states

Present

Today, natural gas accounts for about a quarter of the energy we use.

Natural Gas

About 2,500 years ago, the Chinese recognized that natural gas could be put to work.

The Chinese piped the gas from shallow wells and burnt it under large pans to evaporate

sea water for salt.
3. Sources of Natural Gas

Natural gas can be hard to find since it can be trapped in porous rocks deep underground.
However, various methods have been developed to find out natural gas deposits. The
methods employed are as follows:

1) Looking at surface rocks to find clues about underground formations,

2) Setting off small explosions or drop heavy weights on the surface and record the sound
waves as they bounce back from the rock layers underground and

3) By measuring the gravitational pull of rock masses deep within the earth.

Scientists are also researching new ways to obtain natural (methane) gas from biomass as
a fuel source derived from plant and animal wastes. Methane gas is naturally produced
whenever organic matter decays. Coal beds and landfills are other sources of natural gas,
however only 3 % of the demand is achieved.
Table 2. Production of Natural gas in 2000

Country /countries

Percentage of production to total
production

Russian Federation

22.5

Canada, United Kingdom, Algeria,
Indonesia, Iran, Netherlands, Norway
and Uzbekistan.

Other major production

United States

22.9 %

Natural gas resources are widely distributed around the globe. It is estimated that a
significant amount of natural gas remains to be discovered.

World largest reserves are held by former Soviet Union of about 38 % of total reserves
and Middle East holds about 35 %.

An Introduction to Energy Sources

Table 3. Distribution of proved natural gas reserves (%) in 2004

Country

Reserves

North America

Russian Federation

Middle East

Other Europe and Asia

Asia Pacific

South and central America

Africa

Table 4. Reserves and Resources of Natural Gas

Resources

Reserves

Natural gas resources include all
the deposits of gas that are still in
the ground waiting to be tapped

Natural gas reserves are only those gas deposits
that scientists know, or strongly believe, can be
recovered given today's prices and drilling
technology

4. Physical properties of Natural gas

Natural gas is a mixture of light hydrocarbons including methane, ethane, propane,
butanes and pentanes. Other compounds found in natural gas include CO2, helium,
hydrogen sulphide and nitrogen. The composition of natural gas is never constant,
however, the primary component of natural gas is methane (typically, at least 90%).
Methane is highly flammable, burns easily and almost completely. It emits very little air
pollution. Natural gas is neither corrosive nor toxic, its ignition temperature is high, and it
has a narrow flammability range, making it an inherently safe fossil fuel compared to
other fuel sources. In addition, because of its specific gravity ( 0.60) , lower than that of
air (1.00), natural gas rises if escaping, thus dissipating from the site of any leak.

Natural Gas

5. Classification of Natural Gas

In terms of occurrence, natural gas is classified as non-associated gas, associated gas,
dissolved gas and gas cap.

5.1. Non-associated gas

There is non-associated natural gas which is found in reservoirs in which there is no or, at
best, minimum amounts of crude oil. Non-associated gas is usually richer in methane but
is markedly leaner in terms of the higher paraffinic hydrocarbons and condensate
material. Non-associated gas, unlike associated gas could be kept underground as long as
required. This is therefore discretionary gas to be tapped on the economical and
technological compulsions.

5.2. Associated gas

Natural gas found in crude oil reservoirs and produced during the production of crude oil
is called associated gas. It exists as a free gas (gas cap) in contact with the crude
petroleum and also as a 'dissolved natural gas' in the crude oil. Associated gas is usually
is leaner in methane than the non-associated gas but will be richer in the higher molecular
weight hydrocarbons. Non- associated gas can be produced at higher pressures whereas
associated gas (free or dissolved gas) must be separated from petroleum at lower
separator pressures, which usually involves increased expenditure for compression.

5.3. Classification Based on Gas Composition
Table 5. Classification of Natural Gas Composition

Classification based on
composition

Components

lean gas

Methane

wet gas

considerable amounts of the higher molecular weight
hydrocarbons

sour gas

hydrogen sulphide;

sweet gas

little, if any, hydrogen sulphide;

residue gas

natural gas from which the higher molecular weight
hydrocarbons have been extracted

casing head gas

Derived from petroleum but is separated at the separation
facility at the well head.

An Introduction to Energy Sources 39

6. Natural Gas Products

Natural gas and/or its constituent hydrocarbons are marketed in the form of different
products, such as lean natural gas, wet natural gas (liquefied natural gas (LPG))
compressed natural gas (CNG), natural gas liquids (NFL), liquefied petroleum gas (LPG),
natural gasoline, natural gas condensate, ethane, propane, ethane-propane fraction and
butanes.

6.1. Natural Gas Liquids

Natural gas liquids (NGL) are ethane, propane, and ethane-propane fraction, liquefied
petroleum gas (LPG) and natural gasoline. There are also standards for the natural gas
liquids that are usually set by mutual agreement between the buyer and the seller, but
such specifications do vary widely and can only be given approximate limits. For
example, ethane may have a maximum methane content of 1.58% by volume and
maximum carbon dioxide content of 0.28% by volume. On the other hand, propane will
be specified to have a maximum of 95% propane by volume, a maximum of 1-2% butane
and a maximum vapour pressure which limits ethane content. For butane, the percentage
of one of the butane isomers is usually specified along with the maximum amounts of
propane and pentane.

Other properties that may be specified are vapour pressure, specific gravity, corrosivity,
dryness and sulphur content. The specifications for the propane-butane mixtures will
have limits on the amount of the non-hydrocarbons and in addition, the maximum
isopentane content is usually stated.

The liquefied petroleum gas (LPG) is usually composed of propane, butanes and/or
mixtures thereof, small amounts of ethane and pentane may also be present as impurities.
On the other hand, the natural gasoline (like refinery gasoline) consists of mostly pentane
and higher molecular weight hydrocarbons. The term 'natural gasoline' has also been
applied to mixture of liquefied petroleum gas, pentanes and higher molecular weight
hydrocarbons. Natural gasoline may be sold on the basis of vapour pressure or on the
basis of actual composition which is determined from the Reid vapour pressure (RVP)
composition curves prepared for each product source (ASTM D323).

Natural Gas

6.2. Natural Gas Processing

Natural gas produced at the well contains contaminants and natural gas liquids which
have to be removed before sending to the consumers. These contaminants can cause the
operation problem, pipe rupture or pipe deterioration.

LSJiS LJflSraT.yj.iij:

Gsb
Raaarvalr

Oil

Rasarvolr

Gas-Oil .

Condensate
4*parator

Lasso- or Plant

Dehyl'^le

Remcro
Content Inanta

Con-
dE-ia?:g

Hater.

jaaEL

Hllragen
E*jrac"ilaii

etc

Flam Operations

Dry Gsb
(to Pipeline)

OflMatrksnlzflr

Xl*

M tTp;er

D'y ;^es due:

I 33 B

Fraettormfar [to Pipeline)

* Optional -Step, depenAirj Lfpcn trie source and type of ga& stream

-souroe: Energy ■rrrarmatiDn AamtiKtrartMi, OIDce or Ol and Gas, Natural Gas Dk'tsnr .

, natural Gm
Liquids INGLbi
E:riane
Pippane

3Ua"g

Pentatrfts

\3:jr; SaEO rg

Scheme 1 . Natural gas processing

6.3. Natural Gas Chain

Exploration: Geologists now play a central role in identifying natural gas formations.
They evaluate the structure of the soil and compare it with other areas where natural gas
has been found. Later, they carry out specific tests as studying above ground rock
formations where natural gas traps may have been formed The more accurate these
techniques get the higher the probability of finding gas when drilling.
Extraction: Natural gas is captured by drilling a hole into the reservoir rock. Drilling can
be onshore or offshore. Equipment used for drilling depends on the location of the natural
gas trap and the nature of the rock. Once natural gas has been found it has to be recovered
efficiently. The most efficient recovery rate is characterized by the maximum quantity of
gas that can be extracted during a period of time without damaging the formation. Several

An Introduction to Energy Sources 41

tests must be taken at this stage. Most often, the natural gas is under pressure and will
come out of the hole on its own. In some cases, pumps and other more complicated
procedures are required to remove the natural gas from the ground.

Processing: Processing has been carried out to remove contaminate from the natural gas
and also to convert it in useful energy for its different applications. This processing
involves first the extraction of the natural gas liquids from the natural gas stream and then
the fractioning of the natural gas liquids into their separate components.
7. Transportation

Natural gas reaching the consumers ends normally through pipeline which is normally
made of steel piping and measure between 20 and 42 inches of diameter. Since gas is
moved at high pressures, there are compressor stations along the pipeline in order to
maintain the level of pressure needed. Compared to other energy sources, natural gas
transportation is very efficient because the portion of energy lost from origin to
destination is low.

7.1. Transported as LNG

Natural gas can also be transported by sea. In this case, it is transformed into liquefied
natural gas (LNG). The liquefaction process removes oxygen, carbon dioxide, sulphur
compounds and water. A full LNG chain consists of a liquefaction plant, low temperature
and pressurized transport ships and a regasification terminal.

7.2. Sector wise exploitation of Natural Gas
7.2.1. Residential usage

Natural gas is used in cooking, washing drying, water warming and air conditioning.
Operating costs of natural gas equipment are generally lower than those of other energy
sources.

Natural Gas

7.2.2. Commercial use: The flow diagram for commercial use is shown in
Scheme.2.

Jixploration

< Pioooyybig )

Storage Jp-

( Distribution

Final Users

1 1

.Residential

Commercial 1 Industrial 1

Power Generation

Natural Gas Vehicle?

Scheme 2. Natural gas Chain
7.2.3. Industrial utilization of Natural gas

Manufacture of pulp and paper, metals, chemicals, stone, clay, glass, and to process
certain foods are various fields in which natural gas is effectively utilized. Gas is also
used to treat waste materials, for incineration, drying, dehumidification, heating and
cooling, and CO generation. It is also a suitable chemical feedstock for the petrochemical
industry. Natural gas has a multitude of industrial uses, including providing the base
ingredients for such varied products as plastic, fertilizer, anti-freeze, and fabrics. In fact,
industry is the largest consumer of natural gas, accounting for 43 percent of natural gas
use across all sectors. Natural gas is the second most used energy source in industry,
trailing behind only electricity. Lighting is the main use of energy in the industrial sector,
which accounts for the tremendous electricity requirements of this sector. The graph
below shows current as well as projected energy consumption by fuel in the industrial
sector.

An Introduction to Energy Sources

Electricity, including losses

Natural gas
Oil

1970 1980 1990 2000 2010 2020

Fig.l. Industrial primary energy consumption by Fuel 1970-2020

(Source: EIA Annual Energy Outlook 2002 with Projections to 2020)

Natural gas as a feedstock is commonly found as a building block for methanol, which in
turn has many industrial applications. Natural gas is converted to what is known as
synthesis gas, which is a mixture of hydrogen and carbon oxides formed through a
process known as steam reforming. In this process, natural gas is exposed to a catalyst
that causes oxidization of the natural gas when brought into contact with steam. This
synthesis gas, once formed, may be used to produce methanol (or Methyl Alcohol),
which in turn is used to produce such substances as formaldehyde, acetic acid, and
MTBE (methyl tertiary butyl ether) that is used as an additive for cleaner burning
gasoline. Methanol may also be used as a fuel source in fuel cells.
7.2.4. Power generation

Natural gas works more efficiently and emits less pollution than other fossil fuel power
plants. Due to economic, environmental, and technological changes, natural gas has
become the fuel of choice for new power plants. In fact, in 2000, 23,453 MW
(megawatts) of new electric capacity was added in the U.S. Of this, almost 95 percent, or
22,238 MW were natural gas fired additions. The graph below shows how, according to
the energy information administration (EIA), natural gas fired electricity generation is
expected to increase dramatically over the next 20 years, as all of the new capacity that is
currently being constructed comes online.

Natural Gas

Steam generation units, centralized gas turbines, micro turbines, combined cycle units
and distributed generation are the other examples where natural gas is utilized.

3,500 -

1 1 tutor \

3.000 -

Electricity demand

4M6

2,500 -

1,392

2.000 -

IfiTO

202'.)

I MO -

1,000 - v-

500 -

Projections

;:iT/>

t!)S(>

iMiii

woo

2010

Coal

■ Natural gas

1 Nuclear
1 Renewables

•.Petroleum

2020

Fig. 2. Electricity Generation by Fuel 1970-2020 (billion kilowatt hours)

7.2.5. Transportation

Natural gas can be used as a motor vehicle fuel in two ways: as compressed natural gas
(CNG), which is the most common form, and as liquefied natural gas. Cars using natural
gas are estimated to emit 20% less greenhouse gases than gasoline or diesel cars. In many
countries NGVs are introduced to replace buses, taxis and other public vehicle fleets.
Natural gas in vehicles is inexpensive and convenient.

Most natural gas vehicles operate using compressed natural gas (CNG). This compressed
gas is stored in similar fashion to a car's gasoline tank, attached to the rear, top, or
undercarriage of the vehicle in a tube shaped storage tank. A CNG tank can be filled in a
similar manner, and in a similar amount of time, to a gasoline tank.

Fuel cells: Natural gas is one of the multiple fuels on which fuel cells can operate. Fuel
cells are becoming an increasingly important technology for the generation of electricity.
They are like rechargeable batteries, except instead of using an electric recharger; they
use a fuel, such as natural gas, to generate electric power even when they are in use. Fuel
cells for distributed generation systems offer a multitude of benefits, and are an exciting
area of innovation and research for distributed generation applications. One of the major

An Introduction to Energy Sources

technological innovations with regard to electric generation, whether distributed or

centralized, is the use of Combined Heat and Power (CHP) systems. These systems make

use of heat that is normally wasted in the electric generation process, thereby increasing

the energy efficiency of the total system

8. Chemicals from natural gas: Natural gas a Feed stock for production of value

added products/ Chemicals

Table 6 Methane as chemical feedstock

Product

Reaction

Conditions

Synthesis gas

CH 4 + H 2 -» CO + 3H 2

P: 30-50 bar T: 1123 K
Ni-supported catalyst

Hydrocyanic acid HCN

CH 4 + NH 3 ^ HCN + 3H 2

Degusaa process P: 1 bar
T: 1273 - 1573 K,

CH 4 + NH 3 + I.5O2 ->

Pt catalyst Andrussow process

HCN + 3H 2

P: 1 bar T: 1273-1473K;
Pt catalyst

Chloromethanes

CH 4 xCl 2 -»

T: 673 K; non-catalytic gas

CH 3 C1, CH 2 C1 2

CH 4 . X C1 X + xHCl;

phase reaction

CHCI3, CCU

x = 0-4

Carbon disulphide CS2

CH 4 + 2S 2 -> CS 2 + H 2 S

P; 2.5 bar, T: 873 K

Acetylene Ethylene

2CH4 — > C2H2, C2H4, H2

(a) electric arc process

C2H2, C2H4

(b)partial combustion process

Ethylene and propylene

Oxidative Methane
coupling reaction

Methanol

CH4+O.5 2 -> CH3OH

T: 633-666K

P: 50-150 atm

Catalyst: M0O3 ZnO Fe 2 3

Chloromethane

CH 4 -> CH3CI

T:523KP:230psig
Catalyst: Cu 2 Cl 2 , KC1 and
LaCl 3

Aromatics

H-ZSM-5,Ga-ZSM-5 Al-ZSM-5

Natural Gas

Natural gas find applications a feed stock in chemical industry for producing a number of
methane based and also syngas based products. Natural gas is also an important feed
stock for petrochemicals like ethylene and propylene which are key starting material for
petrochemical industry. Chloromethane, Carbon black proteins are derived from Natural
gas. Hydrogen cyanide, proteins for animal feed are commercially produced from natural
gas or methane. The details of the chemicals that can be derived from methane and the
conditions employed their manufacture are summarized in Table 6.
9. Natural Gas production in India

Over the last decade, natural gas energy sector gained more importance in India. In 1947
production of natural gas was almost negligible, however at present the production level
is of about 87 million standard cubic meters per day (MMSCMD).

Table 7. Production of Petrochemicals from propylene and ethylene which are produced
from Methane - Natural gas as feed stock for petrochemicals

Propylene based

Butene based

Natural Gas

Ethylene based

petrochemicals

liquid as feed
stock

Polypropylene

Secondary butyl

Maleicanhydride

Low density

Isopropyl alcohol

alcohol

Synthesis gas

polyethylene

Acrylonitrile

Butadiene Isobutene

Synthetic natural

High density

Acrylonitrile

Tertiary butyl alcohol

gas

polyethylene

copolymers

Butyl rubber

Ethylene oxide

Acrolein

Vistanes rubber

Ethylene glycols
Ethanol-acetaldehyde
dichloromethane vinyl
chloride

Polyvinyl chloride,
polyvinylalchol
Ethyl benzene styrene
polystyrene

An Introduction to Energy Sources

Oil & Natural Gas Corporation Ltd. (ONGC), Oil India Limited (OIL) and JVs of Tapti,

Panna-Mukta and Ravva are the main producers of Natural gas. Western offshore area is

major contributing area to the total production. The other areas are the on-shore fields in

Assam, Andhra Pradesh and Gujarat States. Smaller quantities of gas are also produced in

Tripura, Tamil Nadu and Rajasthan States.

10. Utilization

Natural gas has been utilized in Assam and Gujarat since the sixties. There was a major

increase in the production and utilization of natural gas in the late seventies with the

development of the Bombay High fields and again in the late eighties when the South

Basin field in the Western Offshore was brought to production. The natural gas supplied

from western offshore fields utilized by Uran in Maharashtra and partly in Gujarat

The gas brought to Hazira is sour gas which has to be sweetened by removing the sulphur

present in the gas. After sweetening, the gas is partly utilized at Hazira and the rest is fed

into the Hazira-Bijaipur-Jagdhishpur (HBJ) pipeline which passes through Gujarat,

Madhya Pradesh, Rajasthan, U.P., Delhi and Haryana. The gas produced in Gujarat,

Assam, etc; is utilized within the respective states.

10.1. Natural Gas as source for LPG

Natural Gas is currently the source of half of the LPG produced in the country. LPG is

now being extracted from gas at Duliajan in Assam, Bijaipur in M.P., Hazira and

Vaghodia in Gujarat, Uran in Maharashtra, Pata in UP and Nagapattinam in Tamil Nadu.

Table 8. All India Region-wise & Sector-wise Gas Supply by GAIL - (2003-04) in
(MMSCMD)

Region/Sector

Power

Fertilizer

S. Iron

Others

Total

HVJ & Ex-Hazira

12.61

13.63

1.24

9.81

37.29

Onshore Gujarat

1.66

1.04

2.08

4.78

Uran

3.57

3.53

1.33

1.41

9.85

K.G. Basin

4.96

1.91

0.38

7.25

Cauvery Basin

1.07

0.25

1.32

Assam

0.41

0.04

0.29

0.74

Tripura

1.37

0.01

1.38

Grand Total

25.65

20.15

2.58

14.23

62.61

48 Natural Gas

Two new plants have also been set up at Lakwa in Assam and at Ussar in Maharastra in
1998-99. One more plant is being set up at Gandhar in Gujarat. Natural gas containing
C2/C3, which is a feedstock for the Petrochemical industry, is currently being used at
Uran for Maharashtra Gas Cracker Complex at Nagothane. GAIL has also set up a 3 lakh
TPA of Ethylene gas based petrochemical complex at Auraiya in 1998-99.
Oil wells are also supplying around 3 MMSCMD in Assam against allocations made by
the Government. Around 8.5 MMSCMD of gas is being directly supplied by the JV
company at market prices to various consumers. This gas is outside the purview of the
Government allocations. In India there is a gap between the production and consumption
level of natural gas. This can be overcome by new discovery and by import or by
combination of both. Natural gas deposits were found in Gulf of Camu and Krishna
Godavari basin, however the consumption cannot be reached by this occurrence. Hence
we have to import the natural gas from east side ( Bangala desh, Indonesia and Malaysia)
and west side ( Iran, Qatar and Saudi Arbia)

10.2. Import of Natural Gas to India through Transnational Gas Pipelines
Iran-Pakistan-India (IPI) Pipeline Project
Myanmar-Bangladesh-India Gas Pipeline Project.

Turkmenistan- Afghanistan-Pakistan (TAP) pipeline

10.3. Liquefied Natural gas

Natural gas at -161 °C transforms into liquid. This is done for easy storage and
transportation since it reduces the volume occupied by gas by a factor of 600. LNG is
transported in specially built ships with cryogenic tanks. It is received at the LNG
receiving terminals and is regassified to be supplied as natural gas to the consumers.
Dedicated gas field development and production, liquefaction plant, transportation in
special vessels, regassification Plant and Transportation & distribution to the Gas
consumer are various steps involved the production and distribution of LNG

10.4. Natural Gas and the Environment

All the fossil fuels, coal, petroleum, and natural gas-release pollutants into the
atmosphere when burnt to provide the energy we need. The list of pollutants they release
reads like a chemical cornucopia-carbon monoxides, reactive hydrocarbons, nitrogen
oxides, sulfur oxides, and solid particulates (ash or soot). The good news is that natural

An Introduction to Energy Sources 49

gas is the most environmentally friendly fossil fuel. It is cleaner burning than coal or
petroleum because it contains less carbon than its fossil fuel cousins. Natural gas also has
less sulfur and nitrogen compounds and it emits less ash particulates into the air when it
is burnt than coal or petroleum fuels.
11. Concluding Remarks

Conversion of coal into other chemicals (especially olefins and other higher
hydrocarbons) is still not economically attractive. So research effort should be made to
convert the available natural gas into value added chemicals. In Indian context, natural
gas can be considered as an alternative source of chemical feedstock for the
petrochemical industries in order to reduce the dependence on imported mineral oil. The
development of an active and selective catalyst is necessary to make the process of
conversion of natural gas into olefins and liquid fuel economically viable. Oxidative
coupling of methane into higher hydrocarbons shows promise in near the future. Natural
gas is one the viable short and middle term energy for transport application along with
its industrial and residential applications.
References

1. B. Viswanathan (Ed.), Natural Gas Prospects and possibilities, The Catalysis
Society of India (1992).

2. R. Narayan and B. Viswanathan, "Chemical and Electrochemical energy

system" Universities press, 1998, pp 28-35.

3. A. Janssen S. F. Lienin, F. Gassmann and W. Alexander "Model aided

policy development for the market penetration of natural gas vehicles in
Switzerland, Transportation Research Part A 40 (2006) 316-333.

4. http://en.wikipedia.org/wiki/Natural gas

5. http://www.indiainfoline.com/refi/feat/gaen.html

6. http://www.eia.doe.gov/oiaf/ieo/nat_gas.html

Chapter - 4

COAL
P. Indra Neel

It's dark as a dungeon and damp as the dew

Where the danger is double and pleasures are few,

Where the rain never falls and the Sun never shines,

It's dark as a dungeon way down in the mine.

Merle Travis

1. Energy - Present and Future

Clearly, energy security and energy independence are the two challenges ahead of any
nation in this new millennium. The global appetite for energy is simply too great and
recurring as well. There is an abrupt need to look something beyond incremental changes
because the additional energy needed is greater than the total of all the energy currently
produced. Energy sources are inevitable for progress and prosperity. Chemistry for sure
holds an answer to the challenges ahead since the whole of the industrial society is based
upon the following two reactions:
C + 2 ^C0 2
H 2 + Vi 2 <-> H 2

All chemical energy systems, in spite of their inherent differences, are related by the fact
that they must involve in some fashion the making and breaking of chemical bonds and
the transformation of chemical structure. A chemist with mastery over chemical
structures, understanding of the nature of the bonds involved between chemical entities
their relative strengths and knowledge of activating C=C, C-C, C-H, C-O, C-N, C-S, H-H
and few other bonds can for sure generate vast reserves of energy conversion as well as
troubleshoot the problems of environmental pollution.

Society is facing with the problem of energy for sustainable development. What chemists
do to address this challenge will have impact reaching far beyond our laboratories and
institutions since all human activities, to name a few, agriculture, transportation,
construction, entertainment, and communication, are energy driven. Food, clothing and

An Introduction to Energy Sources 5 1

shelter are the basic amenities of life. The 21 st Century has dramatized yet another
necessity - The energy. Any small interruption in the availability of energy will have
serious implications on the whole of our complex ways of living. Global energy
consumption and living standards of the raising population are interdependent. It is
predicted that by 2050, i.e., over the next half century, there will be two fold increment in
energy consumption from our current burn rate of 12.8 TW to 28.35 TW.

2. Coal - An age old energy source

Probably coal is one energy source whose utility is devoid of its physical form in a sense
that it can cater to our energy needs either in solid, liquid or gaseous form as the situation
demands. No doubt the heating value changes depending on the amount of hydrogen
present per unit weight but the energy source is unique in a way that it can be moulded in
the hands of a chemist in accordance with the need. The heating value is tunable.
It is not well documented that when exactly the use of coal has started but it is believed
that coal is used for the first time in Europe during Middle Ages.

Just as colours can be classified into primary (red, yellow and blue) and secondary
(suitable combination of primary colours yielding green, purple and orange), fuels can
also be classified as primary and secondary depending on the readiness of their utility.
The major primary fuels are coal, crude petroleum oil and natural gas (contains largely
methane). These are naturally available. Coal and Petroleum are sometimes referred to
as Fossil fuels meaning they were once living matter. Secondary fuels are those derived
from naturally occurring materials by some treatment resulting in drastic and significant
alteration in physical and chemical properties like those of coal gas made from solid coal.
Coal is the most abundant fossil fuel available world wide. Except coal other fossil fuels
resources are limited. Coal is the most abundant fossil fuel on the planet, with current
estimates from 216 years global recoverable reserves to over 500 years at current usage
rates. But the global distribution of coal is non-uniform like any other mineral deposits or
for that matter petroleum. For instance one half of the world's known reserves of coal
are in the United States of America.

3. The genesis of coal

Several significant stages in the conversion of wood to coal are shown schematically in
Fig. 1 . These processes took several millions years to take place.

Coal

Woody material

Cellulose

Lignins

Bacterial action in partly oxidizing environment

Plant Proteins

Oxycellulose, C0 2 , H 2

Partially hydrolyzed

hydrolyzed to amino acids

Conversion to hydrosols and combination, first by physical
attachment and then by chemical combination

"Humic" material, as hydrosols, permeates partly decayed
wood fragments

PEAT-LIKE MATERIAL

Continued bacterial action, including anaerobic

Conversion to hvdrogels

Cover by silts

Consolidation and dewatering

Conversion of hydrosols to hydrogels

Cover by silts, consolidation,
dewatering, continuation
of gel formation

Pressure of overburden, Ageing of gels to form complex "Humic" compounds

the early lignite stage

Pressure, both vertical and lateral + Heat from thrust and friction cause maturing of coals and passage
from gel to solid

In due course, sub-bituminous coals

Pressure, time, heat

Bituminous coals

Semi-bituminous and semi-anthracite

Anthracite

Fig. 1. Schematic diagram of coal genesis (reproduced from ref 6)

An Introduction to Energy Sources

4. Metamorphosis of peat to coal

Coal is formed by the partial decomposition of vegetable matter and is primarily organic
in nature. It is well studied as a sedimentary rock. Coal is a complex organic natural
product that has evolved from precursor materials over millions of years. It is believed
that the formation of coal occurred over geological times in the absence of oxygen there
by promoting the formation of a highly carbonaceous product through the loss of oxygen
and hydrogen from the original precursor molecules. Simplified representation of coal
maturation by inspection of elemental composition is presented in Table 1 .
Table 1. Maturation of coal (reproduced from ref 14)

Composition,

wt%

H/C

Increasing

Wood

1.7

Increasing

pressure,

Peat

1.2

aromatization

temperature,

Lignite coal

0.9

loss of

time

Sub-bituminous coal

0.8

oxygen

' Bituminous coal

0.7 f

Anthracite coal

0.4

Each class implies higher carbon content than the preceding one, e.g., bituminous coals
have greater carbon content than sub-bituminous coals. As shown coals are composed of
C, H, O, N and S. A progressive change in composition is found through the coal rank
series.

Unfortunately, the concept of coal rank series is the largely undefined concept or term
quite often misused by technologists. A coal of a certain level of maturity, or degree of
metamorphosis from the peat, is said to be of certain rank. In US coals are classified not
on the basis of carbon but on depending on the property. The different types of coals
which are clearly recognizable by their different properties and appearance can be
arranged in the order of their increasing metamorphosis from the original peat material.
They are:

Peat

Brown coal
Lignite
Sub-bituminous coal
Bituminous coal
Semi-bituminous coal
Anthracite

Soft coals

Hard coals

54 Coal

The most highly changed material, this is the final member of the series of coals formed
from peat is Anthracite. Each member of the series represents a greater degree of
maturity than the preceding one. The whole is known as the "peat-to-anthracite series".
5. Molecular structure of coal
5.1. Lignite

Lignin structure is preserved in lignites. This means that the macromolecular structure of
lignites would consist of small aromatic units (mainly single rings) joined by cross links
of aliphatic (methylene) chains or aliphatic ethers. If the polymerization were to be
random with cross links heading off in all directions, the structure can be represented as
seen in Fig. 2.

Fig. 2. Sketch of the "Open Structure" with Extensive cross linking and small aromatic
ring systems (reproduced from ref. 4)

5.2. Bituminous coal

Compared to lignites, bituminous coals have higher carbon content and lower oxygen
content. The progression of changes that occur in the structure leads to increase on coal
rank. The structure will be evolved towards graphite.

Viewed edge-on, graphite would be represented as shown in Fig. 3 where the hexagonal
layers are perfectly stacked and aligned.

Fig. 3. A "side ways" view of graphite, showing the perfectly stacked aromatic planes
(reproduced from ref. 4)

The structure of graphite is represented in Fig.4.

An Introduction to Energy Sources

Fig. 4. Layered structure of graphite

Since graphite is a crystalline substance, it produces a characteristic X-ray diffraction
pattern which represents or which is characteristic of the interatomic and inter-planar
distances in the structure. Most coals in contrast, are nearly amorphous and do not
produce sharply-defined X-ray diffraction patterns as graphite. However, when
bituminous coals are examined by X-ray diffraction, it is possible to detect weak
graphite-like signals emerging from the amorphous background. This information
indicates that in bituminous coals the aromatic ring systems are beginning to grow and to
become aligned. The structure of bituminous coals with carbon content in the range of 85
to 91 %, the structure can be represented as depicted in Fig. 5.

Fig. 5. The "liquid structure" of bituminous coals, with reduced cross linking but
increased size of aromatic units relative to the open structure (reproduced from ref 4)

Coal

This is the liquid structure. Compared to the open structure shown earlier, aromatic units
are larger and the cross Unkings are both shorter and fewer in number and some vertical
stacking of the aromatic units is evident.

Some of the configurations understood to exist in coal, giving consideration to aromatic
carbon, hydro aromatic carbon and the kinds of structures and kinds of connecting
bridges which we think join these structures are presented in Fig. 6. It is understood that
bituminous coals consist of layers of condensed aromatic and hydroaromatic clusters
ranging in size from one to several rings per cluster, with an average of three rings per
condensed configuration. The principle types of links or bridges joining these clusters
seem to be short aliphatic chains, some ether linkages, some sulfur linkages, and perhaps
some biphenyl linkages.

c = o

-oXcCC-

H — C — H

"in h

H — C — H

H-C-H

XXX H

„ f O H H

H H-C-H

"•^

H
\

H H

\ /

/ \

H H

H-C-H

H
H

H o'

\ /

-Q-

H H

Fig. 6. Schematic representation of structural groups and connecting bridges in
bituminous coal

An Introduction to Energy Sources 57

5.3. Anthracites

Anthracites have carbon contents over 91%. The structure of anthracite is approaching
that of graphite as represented in Fig. 7. X-ray diffraction data shows increased alignment
of the aromatic rings with little contribution from aliphatic carbon.

Fig. 7. The "anthracite structure", with large, fairly well aligned aromatic units and
minimal cross linking (reproduced from ref. 4)

6. Coal Petrography - The study of macerals

The branch of science concerned with the visible structure of coal is Coal Petrology or
Petrography. The structure may be examined visually by the unaided eye or by optical
microscope. Marie Stopes, a British Scientist, established the foundations of the
discipline of coal petrography. In other words the Petrography can be defined at the
study of coal macerals. In analogy with the minerals of inorganic rock the components of
organic rock i.e., coal, are termed as macerals.

Now the question is what is the use of coal petrography? Or what is the importance of
petrography in coal research and utilization?

The chemical behaviour and reactivity of coal can be predicted with the knowledge of
relative proportions of the different macerals in a coal sample. Different macerals come
from different components of the original plant material which eventually resulted in the
coal. Different plant components have different molecular structures. Substances
having different molecular structures undergo different kinds of chemical reactions under
a given set of conditions. Although plant components are altered chemically during
coalification, the macerals should still reflect some of the chemical differences inherent
of the original plant components. Consequently, one can expect various macerals to show
differences in their chemical behaviour. Thus by knowing the relative proportions of the
different macerals in a coal sample, it should be possible to predict something on the
chemical behaviour and reactivity of the sample.

Coal

There are four types of macro-components in coal as visualized by Stopes namely
Vitrain, Clarain, Durain and Fussian. According to the terminology of Thiessen, these
components correspond to anthraxylon, translucent attritus, opaque attritus and fussain
respectively. In a typical coal seam, 50% of the seam may be clarain, 15-30% durain, 10-
15% vitrain and 1-2% fussain.

i/'i Durain

{d) Fu*aiu

Fig. 8. Sections of Bituminous Coal taken perpendicular to the Bedding Plane

Vitrain: Vitrain is the bright black brittle coal normally occurring in very thin bands. It
fractures conchoidally. It is generally translucent and amber-red in colour. A typical thin
section of vitrain is shown in Fig. 8.

The cells of vitrain consist of complete pieces of bark. Bark tissues are more resistant to
decay. As a result, they form a large proportion of coal than might be expected.
Clarain: Clarain is bright black but less bright than vitrain. It is often finely banded so
that it tends to break irregularly. In thin sections it shows partly the same appearance as
vitrain in thin bands, but these are inter banded with more opaque bands consisting
largely of fragmented plant remains among which can be identified cellular material,

An Introduction to Energy Sources

spore exines and cuticle. A typical clarain structure is shown in Fig. 8. It contains more

plant remains than vitrian and is the commonest of the four types of coal substances.

Durain: Durain is the dull-greyish-black coal which is hard and tough and breaks

irregularly. It is fairly opaque in thin sections and shows large and small pore exines and

woody fragments in a matrix of opaque grains. A typical durain structure with large

flattened macrospores is shown in Fig. 8.

In the coal seam, durain bands are often thick, and can be followed through out the area

of the seam. It is highly charged with durable plant remains and is supposed to be formed

from silts or muds of small particles of vegetable matter.

Fussain: It is soft powdery form occurring in thin seams between the bands of other

types. It is a friable, charcoal like substance which dirties the hand when coal is touched.

It is non-coking but when fines are present in small percentage in coal charge, they help

in increasing the strength of the coke produced there from. Fixed carbon content is

higher and volatile matter is lower in fussain than in other banded ingredients.

7. Constitution of coal

7.1. The variation of oxygen content with rank

100 _

z
c

'/()

BITUMINOUS

UBBITUM1NOUS

LIGNITES

30 20 10

PERCENT OXYGEN

Fig. 9. The variation of oxygen content with rank (reproduced from ref 4)

Coal

There is very large variation of oxygen content as a function of carbon content, from
nearly 30% in the brown coals to ~ 2 in the anthracites. The variation of oxygen content
with rank is illustrated in Fig. 9. It can be learnt that oxygen content and the quality of
coal (rank) are intimately related and as the ranking increases the oxygen content
decrease as seen in the plot. On the weight basis, oxygen is generally the second most
important element in coal. The oxygen content of coal has several practical implications.
The presence of oxygen detracts from the calorific value.

As a rule, for a give amount of carbon, as the oxygen content increases and hydrogen
decreases, the calorific value will drop. This is seen from the values given in Table 2.
Table 2. Effect of oxygen content on calorific value

Compound

H/C

O/C

Heat of combustion, kJ/mole

Methane
Formaldehyde

883
543

Some additional data in support of the above statement are given in Table 3.

Table 3. Effect of increasing oxygen content on heat of combustion of four-carbon-atom
compounds

Compound

Formula

-AH, kJ/mole

Butane

CH3CH2CH2CH3

2880

1-Butanol

CH3CH2CH2CH2OH

2675

2-Butanone

CH3CH2COCH3

2436

Butanoic acid

CH3CH2CH2COOH

2193

Butanedioic acid

HOOCCH2CH2COOH

2156

7.2. The variation of the principal oxygen functional groups with carbon content

The oxygen containing structures represent functional groups, the sites where chemical
reactions occur. The principal oxygen functional groups in coals are carboxylic acids,
phenols, ketones or quinones, and ethers (Fig. 10)

An Introduction to Energy Sources

PHENOLS,

NAPHTHOLS, ETC.

ETHERS

KETONES,
QU1NONES

CARBOXYLICS

RING POSITIONS

OH
I

-OH

k^V^J-H

If
— C — ChL

H 2

II
■C — OH

Fig. 10. Principle oxygen functional groups in coal

Other oxygen functional groups of little importance or absent from coals are esters,
aliphatic alcohols, aldehydes, and peroxides.

The variation of oxygen functional groups as a function of carbon content in vitrinites
(the most common component of coal) is shown in Fig.l 1.

„OTHER

ETHERS

METHOXY ETHERS

70 RO

PERCENT CARBON

9C,

Fig. 11. The variation of principal oxygen functional groups with carbon content
(reproduced from ref. 4)

62 Coal

Methoxy groups are important only in coals with carbon content < 72 wt%. These
groups are derived from lignin, and their loss with increasing coalification suggests that
lignin structures have been completely coalified by the time that the coal has reached
subbituminous rank. Phenols and quinones are the main oxygen groups in the high rank
coals, although some ether may persist in high ranks.

7.3. Determination of fixed carbon content

When coal is heated in an inert atmosphere to about 105 °C, a weight loss occurs. Inert
atmosphere can be either nitrogen or argon preferably. The weight loss is a result of
water being driven off; this weight loss is used to calculate the moisture content of the
sample. If the temperature is increased substantially, to 950 °C under inert atmosphere a
second weight loss is observed. Under these conditions a variety of materials, including
CO2, CO and a mixture of hydrocarbons are evolved. The components emitted during
this experiment are never determined individually. Rather they are lumped together
under the term volatile matter. Thus the weight loss observed at 950 °C provides a
measure of the volatile matter associated with the coal sample. At the end of the volatile
matter test, a black carbonaceous solid still remains. It contains carbon which was not
emitted during the volatile matter determination. If this carbon material remaining from
the volatile matter test is heated in air it burns, leaving behind an incombustible
inorganic, residue, and ash. The ash is collected and weighted.

Three components - moisture, volatile matter and ash - are determined directly. The
fixed carbon is calculated indirectly as:

% FC = 100 - (%M + % VM + % A), where FC = fixed carbon, M = moisture, VM =
volatile matter, A = ash;

7.4. Proximate analysis

A proximate analysis is not approximate analysis! It is unfortunate that the name
proximate sounds much like the word approximate. The procedures for the proximate
analysis are rigorously established by the American Society for testing and materials
(ASTM) along with standards for the acceptable levels of error with in a laboratory and
between different laboratories.

In the above described method of analysis of %M, %VM, %A and there by %FC, the
actual components of the volatile matter, ash or fixed carbon are never determined. That

An Introduction to Energy Sources 63

is, the carbon dioxide evolved in the volatile matter is never collected, determined and

reported as some percentage of CO2. In analytical chemistry the practice of lumping a

variety of components and reporting them as a single entity is called proximate analysis.

The proximate analysis of coal is therefore the determination of moisture of volatile

matter, fixed carbon and ash.

Ash content

Strictly speaking, there is no ash in coal. The incombustible residue, ash, remaining after

the combustion of coal is actually the product of high temperature reactions of inorganic

components, termed as mineral matter, originally present in the coal. It should be noted

that, the amount of ash is not necessarily equal to the amount of original mineral matter.

Fuel ratio of the coal

The fuel ratio of a coal is defined as the ratio of fixed carbon to volatile matter. Coals

with a high volatile matter are usually easy to ignite, burn with a large, often smoky

flame and burn quickly. Coals with high fixed carbon are hard to ignite, but burn slowly

with a short, clean flame.

7.5. Ultimate analysis

The determination of the principal elements of coal, namely, carbon, hydrogen, oxygen,

nitrogen and sulfur is called the ultimate analysis. It is not 'ultimate', in the sense of

determining completely the elemental composition of coal. It is because, the careful

analysis of a coal sample, including the mineral matter, to the trace level would show that

coal contains virtually every element in the periodic table except the rare gases and the

man-made highly, unstable elements and so complete determination of composition and

ultimate analysis are not one and the same which should be borne in mind.

Mineral matter of coal

All elements in coal except C, H, N, O and S will be termed as mineral matter even if

they are present as organometallics, chelates, or absorbed species. Inorganic sulphur and

inorganic oxygen (sulphur and oxygen not present in heteroaromatic structure) will also

be considered as mineral matter.

Iron, silica and alumina constitute the major portion of mineral matter in coal. The four

major groups of mineral matter include alumino-silicates (clay minerals), carbonates,

Coal

sulfides and silicates (mainly quartz). The clay materials are dominant minerals present

in most coals, while pyrite is dominant among sulfides.

Table 4. Mineral matter present in coal (reproduced from ref. 5)

Normal state of combination

% of total

mineral matter

Silica and silicates of aluminium

50-90%

Pyrite (FeS2), ferrous carbonate, ferrous and ferric sulphate and

0-20%

silicates

Carbonate, sulphate and silicates of calcium

0-20%

Carbonate and silicate of magnesium

0-8%

Chloride, carbonate and silicate of sodium and potassium

0-4%

Titanium oxide

0-2%

Carbonate and silicate of manganese

Traces

Sulphur as sulphides and sulphates

0.5-10%

Oxides of phosphorous, gallium, germanium, nickel, beryllium etc.,

<1%

8. Carbonization

The process of heating coals in the absence of air to temperatures at which the coal
decomposes is known as Carbonization. Some coals when carbonized fuse and form a
coal where as others do not. Instead they leave a solid residue on carbonization of
charred material which is of the same shape as the original coal (it has not fused) and is
soft and easily crushed. Even those coals which form fused residues (fused cokes) differ
in the extent to which they do so. They form cokes of different strengths. Coals are
commonly referred to in terms of their ability to form strong coke when carbonized.
They are described as non-caking, weakly caking, or strongly caking. Alternately, they
are said to have poor, or weak, or strong caking properties.
8.1. The caking property

Upon hearing the concept of Caking property the spontaneous questions arise in our mind
are whether it is an advantageous or disadvantageous property and to what extent? What
coal has to do with caking? What gasoline has to do with sweetening? What
'approximate' has to do with proximate analysis? What 'complete' need to do with

An Introduction to Energy Sources 65

ultimate analysis? What does a bomb has to do with calorific value? Does petrography
has any thing to do with petrol? Does the concept of caking imply that coal can be
converted to a delicious, delightful and flexible birthday cake? No!

In Science it is a fallacy or in appropriate terms fashion that with the onslaught of time
the original thoughts or views of the inventor are misinterpreted or manipulated or
misunderstood in many instances for we have no time to go into details and facts and also
short routes are always available in all walks of life whether good or bad. It appears now
that there is a mismatch between the terminology and the property which the terminology
is addressing. The reasons for this in general are not known still. But even now enough
care can be taken by young researchers to look into facts as they mean exactly and as
they implied when they were proposed by the scientists since all the proposals withstood
the test of time, well documented and made available to the needy.

Knowledge of caking properties is essential since this decides the end application of coals
whether it be in the manufacturing of metallurgical coke or in coal-fired furnaces or for
any other specific application. A measure of caking property is necessary for the
classification and selection of coal for different uses. Caking properties influence the
production of coke and the performance of the coal in combustion and gasification.
As a rule caking coals are coals of high volatile, medium volatile and low volatile
bituminous rank. The medium volatile bituminous coals are particularly good caking
coals. Caking coals form an integral part of bituminous family of coal alone. Peat,
lignite, sub-bituminous, semi-anthracite and anthracite are all non-caking.
Coal when heated in an inert atmosphere decomposes with the evolution of a variety of
volatile materials. Some coals pass through a plastic state in which the coal appears to
soften, swell, and then resolidify into a porous mass. Coals which exhibit this behaviour
are called caking coals. When the plastic behaviour is such that the resulting solid
product is a very strong, hard, porous mass, the product is called coke, and the original
coal is called a coking coal. Coke is an important fuel in the metallurgical industry,
particularly in iron and steel industry. Supplies of coking coals are very valuable. All
coking coals are caking coals, but not all caking coals yield a commercially desirable
coke. So, not all caking coals are coking coals.

Coal

8.2. Free Swelling Index

The caking behaviour of a coal is measured in USA by the free swelling index, often
known as FSI. It denotes the caking capacity of coal. In this test a known quantity of
coal is heated in a standard sized crucible under standardized conditions (820 °C for 2.5
minutes). The FSI is determined by comparing the size and shape of the resulting solid
"button" with a series of standard outlines as depicted in Fig. and assigning a value from
1 to 9 at an interval of 0.5. Standard profile of coke buttons numbered from 1 to 9 (at an
interval of 0.5 units) is shown in Fig. 12. An FSI of is assigned to a material which
does not form a coherent mass but rather falls apart when removed from the crucible.
In UK, the caking property is evaluated in terms of British Standard Swelling Number
(BSS No.) Each of these numbers from 1 to 9 at an interval of Vi bear a great
significance as far as the properties and end use of coal are concerned. They indicate the
industrial purpose for which a coal is suitable.

I i 7 C& d^> di> ^_2_> <_A_)

Fig. 12. Standard profiles of the British Standard Swelling Number Test (reproduced
from ref 6)

B.S.S. No. less than 2 ¥2 - Very weak caking properties, or non caking. Coals suitable for

steam raising and other furnaces but unsuitable for any form of carbonization.

B.S.S. No. 3 & 3 V2 - Coals of rather weak to moderate caking power. These are suitable

for all combustion purposes. They are suitable for carbonization in gas-works but

unsuitable for making metallurgical coke.

B.S.S. No. 4-6 V2 - Coals of moderate caking power. These are suitable for combustion

purposes but tend to be rather too strongly caking for some forms of mechanical stokes.

They are very suitable for gas-works and for making second grade metallurgical coke.

An Introduction to Energy Sources

B.S.S. No. 7-9 - Strongly caking coals. These coals are too strongly caking to be really

suitable for combustion to be really suitable for combustion in furnaces and rather too

strongly caking for use in gas works. This range includes the coals which are best for

making metallurgical cokes in coke ovens.

The Bureau of Indian Standards has adopted FSI as one of the tests for caking properties.

The demerits of the test lie in its trial-and-error approach.

9. Coal for the generation of electricity

From coal to electricity generation is not a single step conversion as we see in Fuel cells

where in chemical energy, from any of the hydrocarbon fuels, is directly converted to

electrical energy. The purpose of coal is only to get heat energy. This heat energy in turn

is used to convert water to steam. The steam makes the propeller-like blades of the

turbine to rotate at high speeds. A generator connected to the turbine converts

mechanical energy to electrical energy. The various components and steps involved in

the generation of electricity are depicted in Fig. 13.

The electricity generated is transformed into the higher voltages upto 4,00,000 volts and

used for economic, efficient transmission via power line grids. When it nears the point of

consumption, such as our homes, the electricity is transformed down to the safer 100-250

V used in the domestic market.

Electricity

Coal supply

Stack

Pulvariser/mill

Substation/ transformer

Condenser

Ash system

Water purification
Fig. 13. Schematic representation of the processes taking place in a power plant

68 Coal

Modern pulverized coal combustion technology is well- developed and accounts for over

90% of coal fired capacity world wide. Improvements are being made in the direction of

producing more electricity from less coal being used i.e., to improve the thermal

efficiency of the power station.

9.1. Zero emission power plants - The need of the hour

Zero emission power generation (ZEPG) refers to a range of technologies that are capable

of producing electricity with CO2 emissions that are 10% lower of those from a

conventional planet. Their development is vital for achieving major 50-60% long term

reduction in green house gas emissions.

The significance of the zero emission power plants is well recognized from the statement

of the US President George W. Bush - "Today I am pleased to announce that the United

States will sponsor a $1 billion, 10-year demonstration project to create the worlds first

coal-based, zero-emission electricity and hydrogen power plant ....', on 27 th February,

2003.

Future Gen, a project of US DOE, is viewed as tomorrow's pollution-free power plant. It

is an initiative to build the world's first integrated sequestration and hydrogen production

research power plant.

The goal of the US department of Energy's Future Gen project initiative is to develop and

demonstrate technology for ultra clean 21 st century energy plants that effectively remove

environmental concerns associated with the use of fossil fuels for producing electricity

and simultaneously develop highly efficient and cost-effective power plants. Such

projects truly hold a promise for the safe and ecofriendly utilization of our age old energy

source - Coal.

9.3. Hydrogen content and heating value

Hydrogen is a well-known energy carrier like electricity. Hydrogen content has a role to

play in deciding the heating value per unit of any of the fossil fuels namely coal, oil or

natural gas. Oil and natural gas are considered to be more versatile than coal because of

the higher hydrogen contents they possess in comparison to coal. The hydrogen contents

of coal, oil and natural gas are 7.0, 13 and 25 wt % respectively.

The question one needs to pose is that can we increase the hydrogen content per unit

weight of coal? The answer lies in the processes of gasification and liquefaction of coal

An Introduction to Energy Sources

where in the prime motto is to add hydrogen. The processes of gasification as well as
liquefaction of coal primarily differ in terms of operating conditions. Even though the
chemical reactions operative are different, they are only secondary.

PURE CH„

NATURAL GAS

LPG

NAPHTHA

FUEL OIL
ORDINARY GASOLINE

HIGHLY AROMATIC GASOLINE

CRUDE OIL

RESIDUAL OIL

BITUMINOUS COAL

Fig. 14. Atomic hydrogen/carbon ratios for bituminous coal and other fuels

We are starting with coal, a material that is possessing around 0.8 to 0.9 hydrogen atoms
per carbon atom and we want to produce some thin considerably richer in hydrogen (Fig.
14). In a raw primary liquid fuel produced from coal the hydrogen/carbon ratio on an
atomic basis is about 1.1 to 1.2. If we want a distillate-type fuel, we need a ratio of at
least 1.6.

If it is desired to optimize the production of liquid the production of gases must be
minimized since we need 4 hydrogen atoms per carbon atom to produce methane.
Hydrogen cost is a significantly expensive item in coal liquefaction processes.

70 Coal

10. Coal liquefaction

10.1. Historical background

Is it not surprising to convert a rock into liquid! Coal is quite often termed as a
heterogeneous rock of organic origin containing significant inorganic mineral matter. The
thought of transforming coal into liquid began in 1869 when Bertholet demonstrated that
coal could be hydrogenated. However, it is only with Bergius in 1913, high pressure
hydrogenation and hydrodesulphurization of coal began on practical scale. Bergius
employed the high-pressure technology of the Haber ammonia process to hydrogenate
coal at elevated temperatures and pressure. The major commercial developers of
hydrogenation were I. G. Farben industrie A. G. (I. G. Farben) and BASF. Initial goals
of research at I. G. Farben were to design an effective slurry-phase hydrogenation
catalyst and a sulfur-resistant vapour-phase catalyst that would survive the inherent sulfur
in the coals. The development of a supported catalyst composed on pelleted Mo and Zn
oxides was a breakthrough by Pier in 1926. In 1934, I. G. Farben switched from
Molybdenum to Iron oxide as a slurry-phase catalyst. In slurry phase mode disposable
catalysts such as inexpensive ores, coal minerals and metallic wastes will be employed.
Catalyst self-sufficiency and no concern for catalyst deactivation or recovery are the
advantages in this mode. Slurry - phase catalysts are coal minerals and iron sulfides.
Even though the use of 'a disposable' or a slurry-phase, catalyst in direct coal
liquefaction was initiated in the Bergius process, currently SRC-II technology is being
employed where the presence of recycled coal mineral matter considerably enhanced coal
liquefaction.

10.2. The process of liquefaction of coal

Liquid fuel from coal could be a future alternative to conventional petroleum. From each
ton of coal one to four barrels of oil can be produced. In spite of the vast technology base
for coal liquefaction, the efforts to build commercial plants have subsidized. High capital
costs of synthetic oil plants and declining oil prices were the major obstacles. If costs
would become competitive, coal could be the future source of liquid fuels.
Major issues of concern in the liquefaction of coal are as follows:

1. Process thermal efficiency

2. Hydrogen utilization

An Introduction to Energy Sources

3. Materials and components reliability

4. Solid-liquid separation

5. Product quality and flexibility

6. Feed coal flexibility and

7. Process severity

Among the major areas of concern listed above, the efficient utilization of hydrogen is
one of the critical aspects in direct liquefaction. Effective utilization of hydrogen is
important from the stand point of reaction chemistry, reaction mechanism and economics
of the process. The cost of hydrogen production itself is 1/5 to 1/3 of the direct capital
expenditure of coal liquefaction plants. Hydrogen stabilizers the reactive and unstable
free radicals formed by thermal rupture of chemical bonds of the coal macromolecules.
This prevents the occurrence of retrogressive reactions that produce the undesirable high
molecular weight products that reduce the yield of desired liquid products.
A number of competing parallel reactions may be seen below:

Gas

Coal

Oil
▲

Asphaltene
▲

Coke

Preasphaltene

The overall conversion of coal can be regarded as a series of thermal

decomposition/hydrogenation reactions such as the above. Preasphaltene, Asphaltene

and oil are defined as tetrahydrofuran soluble - toluene insoluble, toluene soluble -

pentane insoluble and pentane soluble coal liquids respectively.

10.3. Catalysis in the liquefaction of coal

One of the important strategies in the process of liquefaction of coal is hydrogen

economy. That is the effective utilization of hydrogen.

Now the question is which is the most efficient method of hydrogen transfer? This is

where the role of catalyst becomes vital in the liquefaction of coal.

A catalyst need to efficiently transfer and distribute hydrogen.

72 Coal

An ideal catalyst should possess the following properties:

1 . High activities for hydrogenation, cracking, and heteroatom removal,

2. Selectivity for maximum liquid yield with minimum gas production,

3. Adequate physical strength to over come mechanical degradation with aging
and regeneration and

4. Resistance to deactivation caused by coke and metal deposition, poisoning,
sintering and pore -mouth blockage.

An effective catalyst should help liquefy coal at lower severity conditions and improve
liquid yield and quality. Catalysts in direct coal liquefaction lower the severity of the
operations essentially by activating both the molecular hydrogen and also the coal
molecules that to at lower reaction temperatures. They improve the product quality by
cracking and reforming heavy molecules to desired products; and removing heteroatoms
(atoms other than C) namely N, O, S from coal and coal liquids.

The advantages offered by catalysts in this regard are many. But all is not easy and
hurdles arise because of the complex nature of coals. Coal, frequently referred as
"Nature's Dump", tends to deactivate the catalyst. Most vital reasons for catalyst
deactivation are coke formation as well as metal deposition apart from poisoning or
sintering which are not as pernicious as those of the former.

Studies reveal that addition of Iron pyrite (FeS2) to coal/oil slurry produces higher
conversion and improved product quality. In quantitative terms addition of five percent
of iron pyrite produces the same increase in conversion as that produced by a 20° C
increase in reaction temperature. Unfortunately, the catalytically active chemical state of
the iron sulfide is not definitely known. Most of the studies strongly suggest that pyrite is
not the active catalyst in coal liquefaction but plays the role of a precursor. Pyrrholite
(Fei.xS, where 0<x<0.125) a non-stoichiometric sulfur-rich crystalline structure, has been
suggested as the catalytically active ingredient in liquefaction. Thus the catalytic action
of pyrite is attributed to its transformation products (pyrrholite and H2S). The critical
parameter in the formation of catalytically active pyrrholite is the partial pressure of H2S.
In addition hydrogen sulfide by itself is catalytically active in the liquefaction of coal.

An Introduction to Energy Sources

10.4. Hydrogen sources

The hydroaromatic portion of coal itself can act as a source for hydrogen. Apart from
this gaseous hydrogen as well as hydrogen-donor solvents can also serve the purpose.
The process of hydrogen addition or hydrogenation can be accomplished either by
catalytic or non-catalytic means. But non-catalytic addition of hydrogen to coal
molecules requires employment of drastic conditions of temperature and pressure. Use of
a catalyst reduces the severity of the process by bringing down the temperature and
pressure. Good hydrogen donor solvents such as 1, 2, 3, 4-tetra hydro naphthalene,
generally known as tetralin, can serve the purpose of supplying hydrogen and stabilizing
the free radicals generated by coal molecules. The reaction can be envisioned as follows

which may proceed sequentially through 1, 2 dihydro naphthalene? The hydrogen
donated by the tetralin is used to cap radicals, thus facilitating coal depolymerization and
liquids production.

However, once the solvent gets depleted of hydrogen it needs to get rehydrogenated
through catalytic means. Tetralin is regenerated as follows:

2 H,

The net process of hydrogenation is represented pictorially as:

+ 2H2

74 Coal

10.5. Coal Blending

Coal blending is a process of mixing two coals of different reactivities. Alternately, coal-
derived ash and/or mineral matter from a reactive coal are added to a less reactive coal.
Coals differ in their liquefaction reactivity due to rank, petrography and concentration of
mineral matte. Addition of a highly reactive coal to a low reactive coal can increase
conversion and lower operating severity in a liquefaction plant. Coal blending is
beneficial in a way that this decreases the severity of plant operating conditions.

10.6. Coal gasification

The steps involved in coal gasification and the products obtained thereby are shown

schematically in Fig. 15.

Ideally it is desirable to gasify coal according to the reaction:

2C + 2H 2 ►CH4 + CO2 AH = 2.765 cal/gram mole

Methane, the principle component of natural gas is produced directly by the above
reaction. Even though a small amount of heat is required for the reaction to sustain as
indicated by the small positive AH (endothermic reaction), several favourable reactions
compete with this reaction making the production of methane indirect. In addition to the
small amount of CH 4 produced directly in the gasifier, the exit gas will contain CO, CO2,
H 2 , H 2 S and H 2 as shown in Fig. 15. Presence of NH 3 depends on whether we use air or
oxygen in the process and the presence of nitrogen in air obviously leads to the evolution
ofNH 3 .

It should be noted that the gasification of the coal takes place in stage 1 itself. The
remaining stages represent processes for the removal of C0 2 and H 2 0, removal of
Sulphur, generally as H 2 S and also ub-grading the heating value of the gas by
methanation. CO and H 2 evolved in stage 1 have no heating value. They undergo water
gas shift reaction in stage 2 as shown below.

CO +H 2 ► C0 2 + H 2

The objective of this operation is to bring the mole ratio of H 2 to CO to a value of 3 to 1.
Once this mole ratio of H 2 and CO is achieved, CO can be converted to CH4 and other
hydrocarbons (Fischer Tropsch synthesis, a process in which CO and hydrogen are
converted to higher hydrocarbons and alcohols on supported cobalt or iron catalyst)
(stage 4).

An Introduction to Energy Sources

The acid gases, H2S and CO2 are removed in stage 3. This is normally done in a wet
collector called a scrubber. Proper choice of a scrubbing liquid allows selective
absorption of H 2 S and CO2.

Stage 1

Stage 2

Stage 3

Stage 4

Stage 5

Gasifier

Coal

Oxygen

Steam

CO, H 2 , C0 2 , H 2 S
NH 3 , H 2 0, CH 4

Water gas shift reactor

Acid gas removal

Methanation

CH 4 ,

Dryer

► H 2

CH 4

Steam

C0 2 , H 2 S

Fig. 15. Schematic representation of various steps in the gasification of coal

Methanation is accomplished in stage 4 by the conversion of CO and H2 according to the
reaction.

CO + 3 H 2 ► CH 4 + H 2 AH = -49,071 cal/grammole

This reaction must be catalyzed to proceed at an economical rate. The large, negative AH
Indicates that the reaction is strongly exothermic and hence cooling must be provided.
The methane produced in stage 4 is referred to as synthetic natural gas (SNG). The
process of drying is carried out in stage 5 where water is eliminated with the objective of
increasing the heating value of the gas. The drying process is carried out by passing them
through agent such as sulfuric acid, calcium chloride, or silica gel. The water vapour is
absorbed by these dehydrating agents.

76 Coal

Normally three kinds of gasifier operations, namely, (1) moving bed gasifier, (2) fixed
fluidized bed and (3) entrained fluidized bed are used.

10.7. In situ gasification of under ground coal

In place or in situ combustion of coal is yet another possible option to extract the heat

energy from coal. This is employed where coal cannot be mined economically or for

those coal deposits remaining after deep mining operations.

Oxygen and steam are piped down to the deposit and the gasified products are brought to

the surface through the wells.

The following are some of the advantages with this form of gasification:

(1) It can be used for un-minable coal deposits, (2) miners health and safety problems are

eliminated, (3) the cost of mining is eliminated, (4) air pollution and solid waste disposal

normally encountered in above-ground gasifications are eliminated.

This process is not devoid of disadvantages. They are as follows: (1) there can be ground

water contamination and gas a leakage problems, (2) it consumes more oxygen per

energy content in the produced gas than in the case of conventional gasifiers, (3) it can

generate only low pressure synthesis gas, and (4) the under ground coal gasification can

be used only for reactive and permeable coals.

This method consists of several steps. First, chemical explosives are used in an array of

drilled holes to fracture a coal bed. Explosions create passages for the flow of

gasification fluids as well as gaseous products. Collection wells would be drilled to the

bottom of the fractured zone. The top would be ignited and a steam-oxygen mixture

would be pumped into the coal vein. The product gases would contain CH 4 , CO, C0 2 ,

H2S and H2 similar to surface gasification operations. This can either be burned for

electric power generation after cleaning or be further processed by methanation to

upgrade its heating value.

10.8. Chemicals from coal

Coal bears significance in terms of producing industrially important chemicals too, apart
from being used as a source of energy. The following table lists the major organic and
inorganic chemicals that can be made from coal. It is known that half the chemicals that
can be obtained are olefins and aromatics.

An Introduction to Energy Sources

Table 5. Some major chemicals derived from coal (reproduced from ref. 3)

Organic chemicals

Inorganic chemicals

Acetic acid

Acetone

Acrylonitrile

Benzene

Carbon tetrachloride

Cumene

Cyclohexane

Ethylene

Ethylene oxide

Formaldehyde

Isopropyl alcohol

Methanol

Perchloroethylene

Phenol

Phthalic anhydride

Propylene

Propylene oxide

Styrene

Toluene

Urea

Vinyl acetate

0-xylene

p-xylene

Ammonia
Sulphuric acid

Current production of chemicals from coal is based on Eastman process. The Eastman
process involves the production of methanol from synthesis gas.

C + H 2 ► CO + H 2

CO + H 2 ► CO2+H2

CO + 2H 2 ► CH3OH

Methonol is reacted with acetic acid to form methyl acetate

CH3COOH + CH3OH ► CH3COOCH3

Methyl acetate can be further reacted with carbon monoxide to form acetic anhydride

CH3COOCH3 + CO ► (CH 3 CO) 2

Acetic acid can be reacted with ethane to make vinyl acetate.

CH 2 =CH 2 + CH3COOH ►CH 2 =CHOOCCH 3

Vinyl acetate can be polymerized to poly(vinyl acetate).

Coal

11. Calorific value and its determination

Calorific value (CV) is defined as the quantity of heat liberated by the combustion of unit

quantity of fuel.

11.1. Determination ofCV

The accurate determination of calorific value requires highly specialized apparatus and

facilities. There is no acceptable, simple means of making this determination. The only

worthwhile determination is that made by a Bomb Calorimeter.

Bomb calorimeter consists of a strong stainless steel vessel, called bomb, capable of with

standing high pressures. The bomb is provided with a lid which can be screwed firmly

on the bomb. The lid in turn is provided with two electrodes and an oxygen inlet valve.

One of the electrodes is provided with a ring to accommodate the silica crucible.

The bomb is placed in a copper calorimeter having a known weight of water. The copper

calorimeter, in turn, is surrounded by an air-jacket and water jacket to prevent loss of heat

due to radiation. The calorimeter is provided with an electrical stirrer for stirring water

and a Beckmann thermometer. The details are shown in Fig. 16.

Seckmann's
thermometer

Electrodes
Mg wire

Crucible

To battery

^Electrically
rZ operated stripper

Bomb

Ring

Weighed sample

Copper calorimeter

Water jacket

Fig. 16. Bomb Calorimeter
Working: A weighted amount of the fuel is placed in the silica crucible. The crucible is
supported over the ring. A fine magnesium write touching the fuel sample is stretched
across the electrodes. Oxygen supply is forced into the bomb till a pressure of 25-30
atmospheres is reached. Initial temperature of the water in the calorimeter is noted after
through stirring. The current is switched on and the fuel in the crucible burns with the

An Introduction to Energy Sources 79

evolution of heat. The heat produced by burning of the fuel is transferred to water which
is stirred throughout the experiment by the electric stirrer. Maximum temperature shown
by thermometer is recorded.

In order to calculate the heat liberated by the combustion of the fuel, the weight of water
in the whole apparatus must be known. Also the amount of heat required to raise all the
parts (metal, glass etc.,) in contact with water through the observed raise in temperature.
This is evaluated in a calibrating experiment. In this a known weight of a pure
hydrocarbon of known calorific value is burned in the apparatus and the raise in
temperature is noted.

11.2. Gross and Net calorific value

The heat evolved by burning the pure substance minus the heat required to raise the
temperature of the water by the observed amount is the heat required to raise the
temperature of the various parts of the apparatus by the same amount. A constant for the
apparatus is derived by dividing this amount of heat by the observed rise in temperature.
This constant is known as water equivalent of the apparatus. It is expressed as the
number of grams of water which are equivalent in heat capacity to the various parts of the
apparatus which are heated by the calorimeter water.

Gross calorific value = the heat evolved (in calories) by a known weight of fuel = the rise
in temperature in degrees centigrade x (water in calorimeter vessel + water in bomb +
water equivalent of the apparatus, all in grams)

11.3. Need for Net calorific value

Calorific values as determined with the bomb calorimeter represent the heat produced by
unit weight of coal when completely oxidized, the products of the combustion (CO2 and
H2O etc.,) being cooled to room temperature. This value is not realized in practice
because the products of combustion are not cooled to room temperature before being
discharged to waste.

Sensible heat is lost in the hot waste products. Apart from this further heat loss occurs in
practice as the latent heat of steam in the hot waste gases. Water is present as such as
moisture in the air-dried coal and a further amount is formed by the combustion of the
hydrogen combined with carbon in the coal. In the bomb calorimeter the moisture is first
evaporated and then condensed to liquid water. Similarly the water formed, as steam; by

80 Coal

combustion is condensed to liquid water, the latent heat of condensation of the steam
being recovered. In industrial practice water from both sources is discharged as steam so
that both latent heat and sensible heat are lost. It is therefore useful to distinguish the
calorific value as determined with the bomb calorimeter by calling it the Gross Calorific
Value.

A lower value can be derived which is the gross calorific value minus the latent heat of
condensation at 15.5 °C of all the water involved. This is named the Net calorific value.
The net calorific value is a more realistic statement of realizable potential heat than the
gross value.

The correction to the gross C.V. is 586 cal/g of water (note that latent heat of steam = 586
cal/g). The water referred to is the weight of water produced by the complete combustion
of unit weight of coal plus the water existing as moisture in the coal. The former is
calculated from a known hydrogen content of the coal.

Net C. V. = Gross C. V. - 586 (water as moisture + water formed from H2) cal/g
It should be noted that the calorific value of coal has been used to exemplify gross and
net calorific value. The same correction can be applied to any fuel of any physical state,
care being taken with the units of weight or volume.
12. Coal burning - Environmental hazards - Measures

Coal is the least hydrogen rich of fossil fuels, meaning that more carbon is oxidized to
CO2 per gram of fuel. In spite of the fact that Coal reserves guarantee energy for over a
century the path is not free from a host of environmental problems in addition to large-
scale CO2 generation that must be addressed. Emissions of NO x from power generation
using coal are an important environmental problem. NO x contributes to the formation of
photochemical smog and acid rain. HCN and NH3 which are formed during pyrolysis of
coal are assumed to be two important precursors for NO x .
12.1. Carbon sequestration

Carbon sequestration is a new way to manage carbon. It is a provision for long-term
storage of carbon in the terrestrial biosphere, underground, or the oceans so that the build
up of C0 2 concentration in the atmosphere can be reduced or slowed down.
Atmospheric levels of CO2 have risen from pre-industrial levels of 280 ppm to present
levels of 375 ppm. This is because of the expanding use of fossil fuels for energy.

An Introduction to Energy Sources 81

Continued increase in carbon emissions are suggested since world can not afford to

abandon fossil fuels. But the technology ultimately going to succeed may be radically

different from today's. New technologies that could capture CO2 either at the point of

emission from the power plants or from the air and dispose it of safely and permanently

are under development. These approaches would make fossil fuel energy use sustainable

for at least another century.

CO2 capture from the air:

This can be accomplished by letting wind carry air over an absorber that pulls off CO2.

This could be achieved through a variety of methods, including blowing air over lime

water, which will remove the CO2 and produce lime stone. The volume of air that needs

to be processed is surprisingly little when compared to the volumes required for

harnessing wind energy.

12.2. CO 2 capture from power plants

The capture of CO2 directly from power plants could be accomplished through new plant

designs. Plant designs that could generate hydrogen or electricity from coal with out any

emissions to the atmosphere are under development. In these methods, lime captures

waste CO2 and generates heat for additional hydrogen production. Captured CO2 can be

disposed by underground injection, a low-cost procedure whose effectiveness has been

proven in enhanced oil recovery. Although underground injection will be more difficult

because the demand for repositories increases this alternate method of disposal is

available. Magnesium silicates can be used to react with CO2 to form Magnesium

carbonate and silica (quartz) which can be disposed safely and permanently.

Norway became the first country to impose a federal tax on atmospheric CO2 emissions

from combustion-based point sources such as coal-fired power plants. The day is not far

off when other countries follow Norway's lead to protect environment and curb raising

temperatures of the planet.

Development of strategies for safe disposal of CO2 waste streams is the need of the hour.

13. Coal - From Indian perspective

Coal is the predominant energy source (58%) in India, followed by oil (27%), natural gas

(7%), lignite (4%), hydropower (3%) and nuclear power (0.22%).

82 Coal

13.1. Coal reserves and mining

India has a long history of commercial coal mining covering nearly 230 years starting
from 1774 by M/s Summer and Heatly of East India Company in the Raniganj coal field
along the western bank of river Damodar.

Major coal fields in India are found in Jharkand, Bihar, West Bengal, Madhya Pradesh,
Maharastra, Assam, Andhra Pradesh, Orissa, Tamil Nadu and Kashmir. Jharia
(Jharkand) and Raniganj (West Bengal) are the biggest and best coalfields of the country.
Unlike the coals in Europe and America, Indian coals have high percentage of mineral
matter, most of which is finely disseminated and intimately mixed with the coal
substance.

Jharkand came into existence on 15 l November 2000 as the 28 l state of India as a result
of the bifurcation of Bihar state. Nearly 32.98 % of coal deposits of India is in Jharkand.
Its mines are in Jharia, Chandrapure, Bokaro, Ramgarh, Kamapur, Charhi and also in
Rajmahal and Daltonganj area.

Raniganj coal field is the largest coalfield in India, belonging to the Gondwana Super
group (Gondwana is a geological term which refers to a certain rock system which is
about 200 million years old. Most of the Indian coals belong to this group.). Mining in
this region dates back to the British period. Unfortunately there are frequent coal-fires
reported from this region and India is loosing good quality coal prior to its exploitation
by spontaneous combustion. Hence there is need for detection and monitoring of coal-
fires in coal fields in order to control them effectively.

Lignite is found mainly at Neyveli in Tamil Nadu. Minor coal fields exist in Andhra
Pradesh, Kashmir and Assam. Assam coals have very high sulphur content (3-8 %).
Kashmir coals are artificial anthracite converted from lignite deposits. Coal deposits of
the Tertiary era (60 million years old) are found in Assam, Rajasthan and Jammu.
14. Conclusion

The time will inevitably come when there will be no more coal and no more petroleum
for the rate at which the reserves are being consumed. Before the disappearance of coal
and petroleum from every day life, mankind must develop a new source of power or
perish. Nuclear energy appears to be a ray of hope even though it requires mutual
cooperation between people world wide in terms of fuel supply and distribution apart

An Introduction to Energy Sources 83

from the intricacies in technological advancement. It is evident that Uranium and
Thorium reserves world wide can match with the man's ever quenching thirst for energy.
Apart from Nuclear Energy, renewable sources such as water, wind and sunlight can also
be thought of as energy sources for future even though in no way they can serve the
needs of common man in the near 100 years of time from now in spite of the toiling
efforts of scientists in this sector.

References

1. Richard Eisenberg and Daniel G. Nocera, Inorg. Chem. 2005, 44, 6799.

2. Jillian L. Dempsey, Arthur J. Esswein, David R. Manke, Joel Rosenthal,
Jake D. Soper and Daniel G. Nocera, Inorg. Chem. 2005, 44, 6879.

3. R. Narayan and B. Viswanathan, Chemical and Electrochemical Energy Systems,
University Press, 1998.

4. Harold H. Schobert, The Chemistry of Hydrocarbon Fuels, Butterworths & Co
(Publishers) Ltd, 1990.

5. O. P. Gupta, Elements of Fuels, Furnaces and Refractories, Khanna Publishers, 1997.

6. J. C. Macrae, An Introduction to the study of fuel, Elsevier Publishing Company,
1966.

7. J. S. S. Brame and J. G. King, Fifth Edition, Rewritten by J. G. King, Fuel - Solid,
Liquid and Gaseous, Edward Arnold (Publishers) Ltd, Fifth Edition, 1955.

8. Bernard R. Cooper, Scientific Problems of Coal Utilization, Proceedings of a
conference at west Virginia Univeristy, May 23-25, 1977, Technical Information
Centre, U. S. Department of Energy, 1978.

9. Mrion L. Shepard, Jack B. Chaddock, Franklin H. Cocks, Charles M. Harman
Introduction to Energy Technology, Ann Arbor Science Publishers Inc, 1976.

10. James Lee Johnson, Kinetics of Coal Gasification, John Wiley & Sons, 1979.

1 1. H. H. Lowry, Chemistry of Coal Utilization, Supplementary Volume,
John Wiley & Sons, Inc, 1963.

12. G. R. Gavalas, Coal Pyrolysis, Coal Science and Technology, Volume 4
Elsevier Scientific Publishing Company, 1982.

84 Coal

13. E. J. Badin, Coal Combustion Chemistry - Correlation Aspects,

Coal Science and Technology, Volume 6, Elsevier Scientific Publishing Company,
1984.

14. A. Volborth, Coal science and chemistry, Coal science and Technology volume 10,
Elsevier Scientific Publishing Company, 1987.

15. Tapas Ranjan Martha, A. Bhattacharya, K. Vinod Kumar, Current Science, 88, No.l,
21,2005.

16. E. Shoko, B. McLellan, A. L. Dicks, J. C. Diniz da Costa, International Journal of
Coal Geology 65(2006)213.

17. A. Verma, A. D. Rao, G. S. Samuelsen, Journal of Power Sources, 158 (2006) 417

18. http://forums.delphiforums.com/chemedu

Chapter - 5

NUCLEAR FISSION

J. Rajeswari

1. Introduction

Energy, 'the ability to do work', is essential for meeting basic human needs, extending life
expectancy and providing comfort in living standards. Energy can be considered in two
categories - primary and secondary. Primary energy is energy in the form of natural
resources, such as wood, coal, oil, natural gas, natural uranium, wind, hydro power, and
sunlight. Secondary energy is the more useable forms to which primary energy may be
converted, such as electricity and petrol. Primary energy can be renewable or non-
renewable: Renewable energy sources include solar, wind and wave energy, biomass
(wood or crops such as sugar), geothermal energy and hydro power. Non-renewable
energy sources include the fossil fuels - coal, oil and natural gas, which together provide
80% of our energy today, plus uranium. The advantages and disadvantages of using
nuclear power are given in Table 1 .
Table 1. Advantages and disadvantages of nuclear power

Advantages

Disadvantages

Nuclear power costs about the same as
coal, so it's not expensive to make.

Although not much waste is produced, it is
dangerous. It must be sealed up and buried
for many years to allow the radioactivity to
die away

Does not produce smoke or carbon dioxide,
so it does not contribute to greenhouse
effect.

Nuclear power is reliable, but a lot of
money has to be spent on safety - if it does
go wrong, a nuclear accident can be a
major disaster

Produces huge amounts of energy from
small amounts of fuel.

Produces small amounts of waste

Nuclear power is reliable

86 Nuclear Fission

To understand the concepts of nuclear reactions, some basic terminologies have to be
understood first. So, the outline of the chapter includes:

(i) Definition of some important terminologies,

(ii) Correlation of binding energy and nuclear fission,

(iii) Definition of nuclear fission and chain reaction,
(iv) Controlled nuclear reaction in nuclear reactors, types of nuclear reactors and

(v) Uncontrollable fission reactions and atom bombs.
2. The nucleus and its constituents

An atom consists of a centrally located nucleus surrounded by electrons revolving in
certain physically permitted orbitals. The nucleus itself is made up of neutrons and
protons, collectively called nucleons. The number of protons (Z) is called the atomic
number and the total number (A) of nucleons in a nucleus is called the atomic (or
nuclear) mass number. The number of neutrons (A-Z) is represented as N. The basic
properties of the atomic constituents are summarized in Table 2
Table 2. Properties of atomic constituents

Fundamental particle

Charge

Mass (u)

Proton

1.007276

Neutron

1.008665

Electron

-e

0.000549

2. a. Charge:

Protons have a positive charge of magnitude e = 1.6022 x 10" 19 C (Coulombs) equal and

opposite to that of the electron. Neutrons are uncharged. Thus, a neutral atom (A, Z)

contains Z electrons and can be written symbolically as a Xn.

2. b. Mass:

Nuclear and atomic masses are expressed in atomic mass units (u), based on the

definition that the mass of a neutral atom of 12 C 6 is exactly 12.000 u

(1 u= 1.6605 xlO" 27 kg).

2. c. Isotopes, isotones and isobars

An Introduction to Energy Sources 87

Atoms are classified as isotopes, isotones, and isobars based on the nuclear contents.

Isobars of an element are atoms whose nuclei have the same Z but different N. They have

similar electron structure and, therefore, similar chemical properties. For example,

hydrogen has three isotopes: H , 2 Hi, 3 H 2 whose nuclei are respectively, the proton p, the

deuteron d, and the triton t. Nuclei with the same N and different Z are called isotones,

and nuclides with the same mass number A are known as isobars. In a symbolic

representation of a nuclear species, or nuclide, it is usual to omit the N and Z subscripts

and include only the mass number as superscript, since A = N + Z and the symbol

representing the chemical element uniquely specifies Z.

2. d. Mass Defect and Binding energy

Careful measurements have shown that the mass of a particular atom is always slightly

less than the sum of the masses of the individual neutrons, protons, and electrons of

which the atom consists. The difference between the mass of the atom and the sum of the

masses of its parts is called the mass defect (Am). The mass defect can be calculated

using equation

Am = [ Z(m P + me) + (A-Z)m„ ] - m alol „ where: Am = mass defect (amu),m„ = mass of a

proton (1.007277 amu),m„ = mass of a neutron (1.008665 amu), m = mass of an

electron (0.000548597 amu),m_ = mass of nuclide \ X (amu), Z = atomic number

(number of protons) and A = mass number (number of nucleons).

In calculating the mass defect it is important to use the full accuracy of mass

measurements because the difference in mass is small compared to the mass of the atom.

Rounding off the masses of atoms and particles to three or four significant digits prior to

the calculation will result in a calculated mass defect of zero.

2. e. Binding energy

Binding energy is the amount of energy that must be supplied to a nucleus to completely

separate its nuclear particles. Binding energy is the energy equivalent of the mass defect.

Binding energy can be calculated by multiplying the mass defect by the factor of 93 1 .5

MeV per amu.

2. f. Binding energy and nuclear stability

As the number of particles in a nucleus increases, the total binding energy also increases.

The rate of increase, however, is not uniform. This lack of uniformity results in a

Nuclear Fission

variation in the amount of binding energy associated with each nucleon within the
nucleus. This variation in the binding energy per nucleon (BE/ A) is easily seen when the
average BE/A is plotted versus atomic mass number (A), as shown in Fig.l.

:-*ij

Fig.l. Nuclear binding energy curve

Fig.l. illustrates that as the atomic mass number increases, the binding energy per
nucleon decreases for A > 60. The BE/A curve reaches a maximum value of 8.79 MeV at
A = 56 and decreases to about 7.6 MeV for A = 238. The general shape of the BE/A
curve can be explained using the general properties of nuclear forces. The nucleus is held
together by very short-range attractive forces that exist between nucleons. On the other
hand, the nucleus is being forced apart by long range repulsive electrostatic (coulomb)
forces that exist between all the protons in the nucleus.

As the atomic number and the atomic mass number increase, the repulsive
electrostatic forces within the nucleus increase due to the greater number of protons in
the heavy elements. To overcome this increased repulsion, the proportion of neutrons
in the nucleus must increase to maintain stability. This increase in the neutron-to-

An Introduction to Energy Sources 89

proton ratio only partially compensates for the growing proton-proton repulsive force
in the heavier, naturally occurring elements. Because the repulsive forces are
increasing, less energy must be supplied, on the average, to remove a nucleon from
the nucleus. The BE/A has decreased. The BE/A of a nucleus is an indication of its
degree of stability. Generally, the more stable nuclides have higher BE/A than the less
stable ones. The increase in the BE/A as the atomic mass number decreases from 260
to 60 is the primary reason for the energy liberation in the fission process. In addition,
the increase in the BE/A as the atomic mass number increases from 1 to 60 is the
reason for the energy liberation in the fusion process, which is the opposite reaction
of fission.

The heaviest nuclei require only a small distortion from a spherical shape (small
energy addition) for the relatively large coulomb forces forcing the two halves of the
nucleus apart to overcome the attractive nuclear forces holding the two halves
together. Consequently, the heaviest nuclei are easily fissionable compared to lighter
nuclei.

3. Radiation and Nuclear Reactions

Traditional chemical reactions occur as a result of the interaction between valence
electrons around an atom's nucleus . In 1896, Henri Becquerel expanded the field of
chemistry to include nuclear changes when he discovered that uranium emitted radiation.
Soon after Becquerel's discovery, Marie Sklodowska Curie began studying radioactivity
and carried out much of the pioneering work on nuclear changes. Curie found that
radiation was proportional to the amount of radioactive element present, and she
proposed that radiation was a property of atoms (as opposed to a chemical property of a
compound ).

In 1902, Frederick Soddy proposed the theory that 'radioactivity is the result of a natural
change of an isotope of one element into an isotope of a different element'. Nuclear
reactions involve changes in particles in an atom's nucleus and thus cause a change in the
atom itself. All elements heavier than bismuth (Bi) (and some lighter) exhibit natural
radioactivity and thus can 'decay' into lighter elements . Unlike normal chemical reactions
that form molecules , nuclear reactions result in the transmutation of one element into a
different isotope or a different element altogether ( the number of protons in an atom

90 Nuclear Fission

defines the element , so a change in protons results in a change in the atom ). There are
three common types of radiation and nuclear changes:

3. a. Alpha Radiation (a) is the emission of an alpha particle from an atom's nucleus .
An a particle contains 2 protons and 2 neutrons (and is similar to a He nucleus: 2 4 He).
When an atom emits an a particle, the atom's atomic mass will decrease by 4 units
(because 2 protons and 2 neutrons are lost) and the atomic number (z) will decrease by 2
units . The element is said to 'transmute' into another element that is 2 units of z smaller.
An example of an a transmutation takes place when uranium decays into the element
thorium (Th) by emitting an alpha particle as depicted in the following equation:

238 TT ^ 4tt„ , 234 t ,

U 92 ► He 2 + Th 9 o

3.b. Beta Radiation (P) is the transmutation of a neutron into a proton and a electron
(followed by the emission of the electron from the atom's nucleus:. i°e). When an atom
emits a P particle, the atom's mass will not change (since there is no change in the total
number of nuclear particles), however the atomic number will increase by 1 (because the
neutron transmutated into an additional proton ). An example of this is the decay of the
isotope of carbon named carbon- 14 into the element nitrogen:

IV, ^ () , 14-KT

C 6 ► e.i + N 7

3. c. Gamma Radiation (y) involves the emission of electromagnetic energy (similar to
light energy ) from an atom's nucleus. No particles are emitted during gamma radiation,
and thus gamma radiation does not itself cause the transmutation of atoms , however y
radiation is often emitted during, and simultaneous to, a or P radioactive decay. X-rays,
emitted during the beta decay of cobalt-60, are a common example of gamma radiation:
3. d. Half-life

Radioactive decay proceeds according to a principal called the half-life . The half-life
(Ty 2 ) is the amount of time necessary for l A of the radioactive material to decay. For
example, the radioactive element bismuth ( 210 Bi) can undergo alpha decay to form the
element thallium ( 206 T1) with a reaction half-life equal to 5 days. If we begin an
experiment starting with lOOg of bismuth in a sealed lead container, after 5 days we will

An Introduction to Energy Sources 91

have 50g of bismuth and 50g of thallium in the jar. After another 5 days (10 from the
starting point), l A of the remaining bismuth will decay and we will be left with 25g of
bismuth and 75 g of thallium in the jar.

The fraction of parent material that remains after radioactive decay can be calculated
using the equation:

Fraction remaining = l/2 n where n = half-lives elapsed
The amount of a radioactive material that remains after a given number of half-lives is
therefore:

Amount remaining = original amount x fraction remaining
The decay reaction and T/ 2 of a substance are specific to the isotope of the element
undergoing radioactive decay. For example, 210 Bi can undergo a decay to 206 T1 with a T/ 2
of 5 days. 215 Bi, by comparison, undergoes P decay to 215 Po with a T/ 2 of 7.6 minutes,
and 208 Bi undergoes yet another mode of radioactive decay (called electron capture) with
a T /2 of 368,000 years!
4. Nuclear fission

Though many elements undergo radioactive decay naturally, nuclear reactions can also be
stimulated artificially. Although these reactions occur naturally, we are most familiar
with them as stimulated reactions. There are 2 such types of nuclear reactions: nuclear
fission and nuclear fusion. This chapter deals exclusively with nuclear fission reaction.
Nuclear Fission denotes reactions in which an atom's nucleus splits into smaller parts,
releasing a large amount of energy in the process (Fig.2). Most commonly, this is done
by 'firing' a neutron at the nucleus of an atom . The energy of the neutron 'bullet' causes
the target element to split into 2 (or more) elements that are lighter than the parent
atom . When a nucleus undergoes fission, it splits into several smaller fragments. These
fragments, or fission products, are about equal to half the original mass. Two or three
neutrons are also emitted. The sum of the masses of these fragments is less than the
original mass. This 'missing' mass (about 0.1 percent of the original mass) has been
converted into energy according to Einstein's equation.

Fission can occur when a nucleus of a heavy atom captures a neutron, or it can
happen spontaneously.

92 Nuclear Fission

NEUTRON

/ f%\ FISSI0N
/ rtrt PRODUCT

NEUTRON J — - 3I9 " J NEUTRON

TARGET \ ^f FISSION
NUCLEUS \ 1 * Cr PRODUCT

NEUTRON

Fig. 2. Nuclear Fission

4. a. Chain Reaction

A chain reaction refers to a process in which neutrons released in fission produce
an additional fission in at least one further nucleus. This nucleus in turn produces
neutrons, and the process repeats (Fig. 3). The process may be controlled (nuclear
power) or uncontrolled (nuclear weapons).

1 st Generation V

2 nd Generation «/ \

/ \

3 r Generation * * <- *

«<JF **J^ *<JP i; r<*r

„th ^ ' > ' \ ' ^ * *

4 Generation * * <-t » * * *

^ 235 u c Neutron

Fig. 3. Nuclear chain reaction

235 U+ n -> fission + 2 or 3 n + 200 MeV

If each neutron releases two more neutrons, then the number of fission doubles each
generation. In that case, in 10 generations there are 1,024 fissions and in 80 generations
about 6 x 10 23 (a mole) fissions.

An Introduction to Energy Sources 93

4. b. Critical Mass

Although two to three neutrons are produced for each fission, not all of these neutrons are
available for continuing the fission reaction. If the conditions are such that the neutrons
are lost at a faster rate than they are formed by fission, the chain reaction will not be self-
sustaining. At the point where the chain reaction can become self-sustaining, this is
referred to as critical mass. In an atomic bomb, a mass of fissile material greater than the
critical mass must be assembled instantaneously and held together for about a millionth
of a second to permit the chain reaction to propagate before the bomb explodes. The
amount of a fissionable material's critical mass depends on several factors; the shape of
the material, its composition and density, and the level of purity. A sphere has the
minimum possible surface area for a given mass, and hence minimizes the leakage of
neutrons. By surrounding the fissionable material with a suitable neutron "reflector", the
loss of neutrons can reduced and the critical mass can be reduced. By using a neutron
reflector, only about 1 1 pounds (5 kilograms) of nearly pure or weapon's grade plutonium
239 or about 33 pounds (15 kilograms) uranium 235 is needed to achieve critical mass.
4. c. U-235 and U-238

Uranium, which is used in nuclear power generation, includes U-235 and U-238. These
two isotopes of uranium, almost like twins, differ only in the number of their neutrons.
When a U-235 atom absorbs a neutron, it loses stability, which causes nuclear fission.
Nuclear power generation utilizes thermal energy emitted at the time of nuclear fission. A
U-238 nucleus, on the other hand, does not split when a neutron is absorbed; instead U-
238 changes into plutonium 239.
4. d. Uranium Enrichment

The concentration of U-235, with which nuclear fission occurs, is increased from
approximately 0.7% to 3-5%. Enrichment methods include the gaseous diffusion process,
the laser enrichment method, and the centrifuge process.
4. e. Controlled Nuclear Fission and Nuclear Reactors

To maintain a sustained controlled nuclear reaction, for every 2 or 3 neutrons
released, only one must be allowed to strike another uranium nucleus (Fig.4). If this
ratio is less than one then the reaction will die out; if it is greater than one it will
grow uncontrolled (an atomic explosion). A neutron absorbing element must be

94 Nuclear Fission

present to control the amount of free neutrons in the reaction space. Most reactors
are controlled by means of control rods that are made of a strongly neutron-
absorbent material such as boron or cadmium.

ABSORBED
URANIUM NUCLEI , ML -JT r ' NEUTRON

INITIAL
NEUTRON

ABSORBED NEUTRON

Fig. 4. Controlled Nuclear fission

There are different types of nuclear reactors such as pressurized water reactor (Fig. 5),
boiling water reactor, gas cooled reactor, pressurized heavy water reactor, light water
graphite reactor and so on. Most are used for power generation, but some can also
produce plutonium for weapons and fuel. Two components are common to all reactors,
control rods and a coolant. Control rods determine the rate of fission by regulating the
number of neutrons. These rods consist of neutron-absorbing elements such as boron.
These are made with neutron-absorbing material such as cadmium, hafnium or boron, and
are inserted or withdrawn from the core to control the rate of reaction, or to halt it.
(Secondary shutdown systems involve adding other neutron absorbers, usually as a fluid,
to the system.) The coolant removes the heat generated by fission reactions. Water is the
most common coolant, but pressurized water, helium gas, and liquid sodium have been
used. In light water reactors the moderator functions also as coolant.
In addition to the need to capture neutrons, the neutrons often have too much kinetic
energy. These fast neutrons are slowed through the use of a moderator such as heavy
water and ordinary water. Some reactors use graphite as a moderator, but this design as
several problems. Once the fast neutrons have been slowed, they are more likely to
produce further nuclear fissions or be absorbed by the control rod.

An Introduction to Energy Sources

CONTAINMENT

ELECTRICITY
GENERATOR

Fig. 5. Pressurized water reactor

Slow-neutron reactors operate on the principle that uranium-235 undergoes fission more
readily with thermal or slow neutrons. Therefore, these reactors require a moderator to
slow neutrons from high speeds upon emerging from fission reactions. The most common
moderators are graphite (carbon), light water (H 2 0), and heavy water (D 2 0). Since slow
reactors are highly efficient in producing fission in uranium-235, slow-neutron reactors
operate with natural or slightly enriched uranium. Light-water reactors are classified as
either pressurized-water reactors (PWR) or boiling-water reactors (BWR), depending on
whether the coolant water is kept under pressure or not. The long time periods, typically
12 to 18 months, between refueling of light-water reactors make it difficult to use them as
a source of plutonium.
5. Fast Breeder Reactor

The fast breeder or fast breeder reactor (FBR) is a fast neutron reactor designed to breed
fuel by producing more fissile material than it consumes. They are supposed to minimize

96 Nuclear Fission

the nuclear wastes. The FBRs usually use a mixed oxide fuel core of up to 20%
plutonium dioxide (PuCh) and at least 80% uranium dioxide (UO2). The plutonium used
can be from reprocessed civil or dismantled nuclear weapons sources. Surrounding the
reactor core is a blanket of tubes containing non- fissile uranium-238 which, by capturing
fast neutrons from the reaction in the core, is partially converted to fissile plutonium 239
(as is some of the uranium in the core), which can then be reprocessed for use as nuclear
fuel. No moderator is required as the reactions proceed well with fast neutrons. Early
FBRs used metallic fuel, either highly enriched uranium or plutonium .
Fast reactors typically use liquid metal as the primary coolant, to cool the core and heat
the water used to power the electricity generating turbines. Sodium is the normal coolant
for large power stations, but lead and Na-K have both been used successfully for smaller
generating rigs. Some early FBRs used mercury . One advantage of mercury and Na-K is
that they are both liquids at room temperature, which is convenient for experimental rigs
but less important for pilot or full scale power stations. At its best, the Breeder Reactor
system produces no nuclear waste whatever - literally everything eventually gets used. In
the real world, there actually may be some residual material that could be considered
waste, but its half-life - the period of time it takes for half the radioactivity to dissipate -
is of the order of thirty to forty years.

India has an active development programme featuring both fast and thermal breeder
reactors . India's first 40 MWt Fast Breeder Test Reactor (FBTR) attained criticality on
18th October 1985. Thus India becomes the sixth nation having the technology to built
and operate a FBTR after US, UK, France, Japan and the former USSR. India has
developed and mastered the technology to produce the plutonium rich U-Pu mixed
carbide fuel. This can be used in the Fast Breeder Reactor. India has consciously
proceeded to explore the possibility of tapping nuclear energy for the purpose of power
generation and the Atomic Energy Act was framed and implemented with the set
objectives of using two naturally occurring elements Uranium and Thorium having good
potential to be utilized as nuclear fuel in Indian Nuclear Power Reactors. The estimated
natural deposits of these elements in India are:

• Natural Uranium deposits - -70,000 tonnes

• Thorium deposits - ~ 3,60,000 tonnes

An Introduction to Energy Sources 97

Indian nuclear power generation envisages a three stage program. Stage 1 has natural
uranium dioxide as fuel matrix and heavy water as both coolant and moderator. In this
stage, U-235 gives several fission products and tremendous amount of energy and U-238
gives Pu-239. India's second stage of nuclear power generation envisages the use of Pu-
239 (main fissile material in stage 2) obtained from the first stage reactor operation, as
the fuel core in fast breeder reactors. A blanket of U-238 surrounding the fuel core will
undergo nuclear transmutation to produce fresh Pu-239 as more and more Pu-239 is
consumed during the operation. Besides a blanket of Th-232 around the FBR core also
undergoes neutron capture reactions leading to the formation of U-233. U-233 is the
nuclear reactor fuel for the third stage of India's Nuclear Power Programme. It is
technically feasible to produce sustained energy output of 420 GWe from FBR. The third
phase of India's Nuclear Power Generation programme is, breeder reactors using U-233
fuel. India's vast thorium deposits permit design and operation of U-233 fuelled breeder
reactors. U-233 is obtained from the nuclear transmutation of Th-232 used as a blanket
in the second phase Pu-239 fuelled FBR. Besides, U-233 fuelled breeder reactors will
have a Th-232 blanket around the U-233 reactor core which will generate more U-233 as
the reactor goes operational thus resulting in the production of more and more U-233 fuel
from the Th-232 blanket as more of the U-233 in the fuel core is consumed helping to
sustain the long term power generation fuel requirement. These U-233/Th-232 based
breeder reactors are under development and would serve as the mainstay of the final
thorium utilization stage of the Indian nuclear programme. The currently known Indian
thorium reserves amount to 358,000 GWe-yr of electrical energy and can easily meet the
energy requirements during the next century and beyond.
6. From Fission to Electricity

Nuclear power is the controlled use of nuclear reactions (currently limited to nuclear
fission and radioactive decay ) to do useful work including propulsion, heat, and the
generation of electricity. Nuclear energy is produced when a fissile material, such as
uranium -235, is concentrated such that the natural rate of radioactive decay is accelerated
in a controlled chain reaction and creates heat - which is used to boil water, produce
steam, and drive a steam turbine. The turbine can be used for mechanical work and also
to generate electricity .

98 Nuclear Fission

During the fission of U-235, 3 neutrons are released in addition to the two daughter
atoms . If these released neutrons collide with nearby U235 nuclei, they can stimulate the
fission of these atoms and start a self-sustaining nuclear chain reaction. This chain
reaction is the basis of nuclear power. As uranium atoms continue to split, a significant
amount of energy is released from the reaction. The heat released during this reaction is
harvested and used to generate electrical energy . A nuclear power plant produces
electricity in almost exactly the same way that a conventional (fossil fuel) power plant
does. A conventional power plant burns fuel to create heat. The fuel is generally coal, but
oil is also sometimes used. The heat is used to raise the temperature of water, thus
causing it to boil. The high temperature and intense pressure steam those results from the
boiling of the water turns a turbine, which then generates electricity. A nuclear power
plant works the same way, except that the heat used to boil the water is produced by a
nuclear fission reaction using 235U as fuel, not the combustion of fossil fuels. A nuclear
power plant uses less fuel than a comparable fossil fuel plant. A rough estimate is that it
takes 17,000 kilograms of coal to produce the same amount of electricity as 1 kilogram of
nuclear uranium fuel.
7. Spontaneous Nuclear Fission - Nuclear weapons

FISSION NUCLEUS

FISSION PRODUCT FISSION PRODUCT

Fig. 6. Spontaneous nuclear fission

The spontaneous nuclear fission rate (Fig. 6) is the probability per second that a given
atom will fission spontaneously, that is, without any external intervention. If a
spontaneous fission occurs before the bomb is fully ready, it could fizzle. Plutonium 239
has a very high spontaneous fission rate compared to the spontaneous fission rate of
uranium 235. Scientists had to consider the spontaneous fission rate of each material

An Introduction to Energy Sources

when designing nuclear weapons. Nuclear weapon is a weapon which derives its
destructive force from nuclear reactions of either nuclear fission or the more powerful
fusion . Nuclear weapons have been used only twice, both during the closing days of
World War II . The first event occurred on the morning of 6 August 1945 , when the
United States dropped a uranium gun-type device code -named " Little Boy " on the
Japanese city of Hiroshima . The second event occurred three days later when a plutonium
implosion-type device code -named " Fat Man " was dropped on the city of Nagasaki . In
fission weapons, a mass of fissile material ( enriched uranium or plutonium) is rapidly
assembled into a supercritical mass by shooting one piece of sub-critical material into
another or compressing a sub-critical mass, usually with chemical explosives. Neutrons
are then injected to start a chain reaction that grows rapidly and exponentially , releasing
tremendous amounts of energy. A major challenge in all nuclear weapon designs is
ensuring that a significant fraction of the fuel is consumed before the weapon destroys
itself.
7. a. Little Boy: A Gun-Type Bomb

GUN BARREL CASING

NEUTRON TRIGGER

HIGH- ENERGY CHEMICAL EXPLOSIVE

Fig. 7. little boy - first nuclear weapon

In essence, the Little Boy design (Fig. 7) consisted of a gun that fired one mass of
uranium 235 at another mass of uranium 235, thus creating a supercritical mass. A
crucial requirement was that the pieces be brought together in a time shorter than the

100

Nuclear Fission

time between spontaneous fissions. Little Boy was the first nuclear weapon used in
warfare. Once the two pieces of uranium are brought together, the initiator
introduces a burst of neutrons and the chain reaction begins, continuing until the
energy released becomes so great that the bomb simply blows itself apart.
7. B.Time of Reaction

The released neutron travels at speeds of about 10 million meters per second, or
about 3% the speed of light. The characteristic time for a generation is roughly the
time required to cross the diameter of the sphere of fissionable material. A critical
mass of uranium is about the size of a baseball (0.1 meters). The time, T, the neutron
would take to cross the sphere is:

T = 0.1 ml lxlO 7 ms" 1 = lxlO 8 sec
The complete process of a bomb explosion is about 80 times this number, or about a
microsecond.

INITIATOR

CHEMICAL EXPLOSIVES

PLUTONIUM - 23

DETONATORS

TAMPER OF URANIUM - 238

Fig. 8. Implosion type bomb (the second nuclear weapon)

7. d. Fat Man: Implosion-Type Bomb

"Fat-Man"(Fig.8) was the codename of the atomic bomb which was detonated over
Nagasaki , Japan by the United States , on August 9 , 1945 . It was the second of the
two nuclear weapons to be used in warfare . The initial design for the plutonium

An Introduction to Energy Sources 101

bomb was also based on using a simple gun design (known as the "Thin Man") like
the uranium bomb. As the plutonium was produced in the nuclear reactors at
Hanford, Washington, it was discovered that the plutonium was not as pure as the
initial samples from Lawrence's Radiation Laboratory. The plutonium contained
amounts of plutonium 240, an isotope with a rapid spontaneous fission rate. This
necessitated that a different type of bomb be designed. A gun-type bomb would not
be fast enough to work. Before the bomb could be assembled, a few stray neutrons
would have been emitted from the spontaneous fissions, and these would start a
premature chain reaction, leading to a great reduction in the energy released.
References:

1 . J. Lilley, Nuclear Physics, John Wiley & Sons, Chichester (2001).

2. K. S. Krane, Introductory Nuclear Physics, John Wiley & Sons, New York
(1998).

3. M. N. Sastri, Introduction to Nuclear Science, Affiliated East - West Press
Private Limited, New Delhi (1983).

4. www.uic.com

5. http://en.wikipedia.org/wiki/Nuclear_power

6. http://www.visionlearning.com/library/module_viewer .php?mid=59

7. http://www.barc.ernet.in/webpages/about/anul.htm

Chapter - 6
NUCLEAR FUSION
P. Satyananda Kishore

1 . Introduction

Why there is a need for alternative energy resources derived from nuclear reactions?
The World, particularly developing countries, needs a New Energy Source because of

• Growth in world population and growth in energy demand from increased
industrialization/affluence which will lead to an Energy Gap that will be
increasingly difficult to fulfill with fossil fuels

• Without improvements in efficiency we will need 80% more energy by 2020

• Even with efficiency improvements at the limit of technology we would still need
40% more energy

Incentives for Developing Fusion

• Fusion powers the Sun and the stars

- It is now within reach for use on Earth

• In the fusion process lighter elements are "fused" together, making heavier
elements and producing prodigious amounts of energy

• Fusion offers very attractive features:

- Sustainable energy source

- No emission of Greenhouse or other polluting gases

- No risk of a severe accident

- No long-lived radioactive waste

• Fusion energy can be used to produce electricity and hydrogen, and for
desalination

Fusion produces radio active waste volumes more than fission but much less than coal for

power plants of equal size.

2. Nuclear Fusion

Nuclear fusion is the process by which two nuclei join together to form a heavier nucleus.

It is accompanied by the release or absorption of energy depending on the masses of the

nuclei involved. Iron and nickel nuclei have the largest binding energies per nucleon of

An Introduction to Energy Sources 103

all nuclei and therefore are the most stable. The fusion of two nuclei lighter than iron or
nickel generally releases energy while the fusion of nuclei heavier than them absorbs
energy.

Nuclear fusion of light elements releases the energy that causes stars to shine and
hydrogen bombs to explode. Nuclear fusion of heavy elements (absorbing energy) occurs
in the extremely high-energy conditions of supernova explosions. Nuclear fusion in stars
and supernovae is the primary process by which new natural elements are created. It is
this reaction that is harnessed in fusion power . In the core of the Sun, at temperatures of
10-15 million Kelvin, Hydrogen is converted to Helium by fusion - providing enough
energy to keep the Sun burning and to sustain life on Earth

A vigorous world-wide research programme is underway, aimed at harnessing fusion
energy to produce electricity on Earth. If successful, this will offer a viable alternative
energy supply within the next 30-40 years with significant environmental, supply and
safety advantages over present energy sources

To harness fusion on Earth, different, more efficient fusion reactions than those at work
in the Sun are chosen; those between the two heavy forms of Hydrogen : Deuterium (D)
and Tritium (T). All forms of Hydrogen contain one proton and one electron. Protium,
the common form of Hydrogen has no neutrons, Deuterium has one neutron, and Tritium
has two. If forced together, the Deuterium and Tritium nuclei fuse and then break apart to
form a helium nucleus (two protons and two neutrons) and an uncharged neutron. The
excess energy from the fusion reaction (released because the products of the reaction are
bound together in a more stable way than the reactants) is mostly contained in the free
neutron.

Deuterium and/or Tritium fuse according to the following equations

• 2 iH + 2 iH -> 3 2 He + \n

• 2 Ji + 3 iH -> 4 2 He + V

Great potential for meeting our energy needs: 1 g of H 2 produces energy equivalent from

burning 1 ton of coal.

Deuterium is naturally occurring and is available at 0.015% abundance. 2 iH in water

could meet energy needs for millions of years.

Tritium is radioactive and must be produced via fission of Li (abundant in earth's crust).

104

Nuclear Fusion

6 3 Li + 'n -> 4 2 He + 3 iH

For example, 10 grams of Deuterium which can be extracted from 500 L (or 0.5 Mg) of
water and 15g of Tritium produced from 30g of Lithium would produce enough fuel for
the lifetime electricity needs of an average person in an industrialized country.
Sustained Fusion Requirements

• Extremely high temperatures (100 - 200 million K) at which the hydrogen
isotopes are stripped of their electrons creating a plasma of hot charged gases.

• Control of plasma to confine the energy for 1-2 seconds.

• Extremely high pressure to force the cations closer than 10" 15 m to achieve plasma
density > 2E20 particles/m 3

For potential nuclear energy sources for the Earth, the deuterium-tritium fusion reaction
contained by some kind of magnetic confinement seems the most likely path. However,
for the fueling of the stars , other fusion reactions will dominate.

tot toKSfv"

I*'

H-g

T^S

D*4tftTMi>l"iWp.rn

F>3Kn

2.1. Deuterium - tritium fusion reaction:

D + T — > 4 He + n + Energy

tritium H 3

helium He 4

*>, ' S

Fusion

/-^^\

•J

deuterium H^

neutron

An Introduction to Energy Sources

105

The He nuclei ('a' particles) carry about 20% of the energy and stay in the plasma. The
other 80% is carried away by the neutrons and can be used to generate steam.
It takes considerable energy to force nuclei to fuse, even those of the least massive
element, hydrogen . But the fusion of lighter nuclei, which creates a heavier nucleus and a
free neutron , will generally release more energy than it took to force them together — an
exothermic process that can produce self-sustaining reactions.

The energy released in most nuclear reactions is larger than that for chemical
reactions, because the binding energy that holds a nucleus together is far greater than the
energy that holds electrons to a nucleus. For example, the ionization energy gained by
adding an electron to a hydrogen nucleus is 13.6 electron volts less than one-millionth of
the 17 MeV released in the D-T (deuterium-tritium) reaction .
2.2. Comparison of energies released from various processes
Fusion occurs at a sufficient rate only at very high energies (temperatures); on earth,
temperatures greater than 100 million Kelvin is required. At these extreme
temperatures, the Deuterium - Tritium (D-T) gas mixture becomes plasma (a hot,
electrically charged gas). In plasma, the atoms become separated - electrons have been
stripped from the atomic nuclei (called the "ions"). For the positively charged ions to
fuse, the temperature (or energy) must be sufficient to overcome their natural charge
repulsion.

Chemical

Fission

Fusion

Reaction

C+0 2 ^ C0 2

U-235

2 jH + 2 Ji -> 3 2 He + \n

Starting Material

coal

U0 2 ore

H-2, H-3 isotopes

Temp needed

700 K

1000 K

1E+8K

Energy
J/kg fuel

3.3E+7 or
33 MegaJ

2.1E+12or
2000 GigaJ

3.4E+14 or
3400000 GigaJ

In order to harness fusion energy, scientists and engineers are learning how to control
very high temperature plasmas. The use of much lower temperature plasmas are now
widely used in industry, especially for semi-conductor manufacture. However, the control

106

Nuclear Fusion

of high temperature fusion plasmas presents several major science and engineering
challenges - how to heat a plasma to in excess of 100 million Kelvin and how to confine
such a plasma, sustaining it so that the fusion reaction can become established.
2.3. Conditions for a Fusion Reaction

Three parameters (plasma temperature, density and confinement time) need to be
simultaneously achieved for sustained fusion to occur in plasma. The product of these is
called the fusion (or triple) product and, for D-T fusion to occur, this product has to
exceed a certain quantity - derived from the so-called Lawson Criterion after British
scientist John Lawson who formulated it in 1955.

Once a critical ignition temperature for nuclear fusion has been achieved, it must
be maintained at that temperature for a long enough confinement time at a high enough
ion density to obtain a net yield of energy. In 1957, J. D. Lawson showed that the product
of ion density and confinement time determined the minimum conditions for productive
fusion, and that product is commonly called Lawson's criterion. Commonly quoted
figures for this criterion are

Lawson's Criterion for fusion

ni> 10 14 s/cm 3

deuterium-tritium fusion

ni> 10 16 s/cm 3

Deuterium-deuterium fusion

The closest approach to Lawson's criterion has been at the Tokamak Fusion Test Reactor

(TFTR) at Princeton. It has reached ignition temperature and gotten very close to

Lawson's criterion, although not at the same time.

Attaining conditions to satisfy the Lawson criterion ensures the plasma exceeds Break

even - the point where the fusion power out exceeds the power required to heat and

sustain the plasma.

2.3.1. Temperature

Fusion reactions occur at a sufficient rate only at very high temperatures - when the

positively charged plasma can overcome their natural repulsive forces. Typically, in JET,

over 100 million Kelvin is needed for the Deuterium- Tritium reaction to occur; other

fusion reactions (e.g. D-D, D-He 3 ) require even higher temperatures.

An Introduction to Energy Sources 107

2.3.2. Density

The density of fuel ions (the number per cubic metre) must be sufficiently large for
fusion reactions to take place at the required rate. The fusion power generated is reduced
if the fuel is diluted by impurity atoms or by the accumulation of Helium ions from the
fusion reaction itself As fuel ions are burnt in the fusion process they must be replaced
by new fuel and the Helium products (the "ash") must be removed.

2.3.3. Energy Confinement

The Energy Confinement Time is a measure of how long the energy in the plasma is
retained before being lost. It is officially defined as the ratio of the thermal energy
contained in the plasma and the power input required to maintain these conditions.
Magnetic fields are used to isolate the very hot plasma from the relatively cold vessel
walls in order to retain the energy for as long as possible. Losses in magnetically-
confined plasma are mainly due to radiation. The confinement time increases
dramatically with plasma size (large volumes retain heat better than small volumes) the
ultimate example being the Sun whose energy confinement time is massive.
For sustained fusion to occur, the following plasma conditions need to be maintained
(simultaneously).

* Plasma temperature: (T) 100-200 million Kelvin

* Energy Confinement Time: (t) 1-2 seconds

* Central Density in Plasma: (n) 2-3 x 10 20 particles m" 3 (approx. 1/1000 gram m" 3 ).

2.3.4. Magnetic plasma confinement

Since a plasma comprises charged particles : ions (positive) and electrons (negative),
powerful magnetic fields can be used to isolate the plasma from the walls of the
containment vessel; thus enabling the plasma to be heated to temperatures in excess of
100 million Kelvin. This isolation of the plasma reduces the conductive heat loss through
the vessel and also minimizes the release of impurities from the vessel walls into the
plasma that would contaminate and further cool the plasma by radiation.
In a magnetic field the charged plasma particles are forced to spiral along the magnetic
field lines. The most promising magnetic confinement systems are toroidal (from torus :
ring-shaped) and, of these, the most advanced is the Tokamak. Currently, JET is the
largest Tokamak in the world although the future ITER machine will be even larger.

108 Nuclear Fusion

Other, non magnetic plasma confinement systems are being investigated - notably inertial
confinement or laser-induced fusion systems

The plasma is heated in a ring-shaped vessel (or torus) and kept away from the vessel
walls by the applied magnetic fields. The basic components of magnetic confinement
system are:-

• The toroidal field - which produces a field around the torus. This is maintained by
magnetic field coils surrounding the vacuum vessel. The toroidal field provides
the primary mechanism of confinement of the plasma particles.

• The poloidal field - which produces a field around the plasma cross section. It
pinches the plasma away from the walls and maintains the plasma's shape and
stability. The poloidal field is induced both internally, by the current driven in the
plasma (one of the plasma heating mechanisms), and externally, by coils that are
positioned around the perimeter of the vessel.

The main plasma current is induced in the plasma by the action of a large transformer. A

changing current in the primary winding or solenoid (a multi turn coil wound onto a large

iron core in JET) induces a powerful current (up to 5 Million Amperes on JET) in the

plasma - which acts as the transformer secondary circuit

One of the main requirements for fusion is to heat the plasma particles to very high

temperatures or energies. The following methods are typically used to heat the plasma -

all of them are employed on JET .

3. Principle methods of heating plasma:

3.1. Ohmic Heating and Current Drive

Currents up to 5 million amperes (5MA) are induced in the JET plasma - typically via the
transformer or solenoid. As well as providing a natural pinching of the plasma column
away from the walls, the current inherently heats the plasma - by energizing plasma
electrons and ions in a particular toroidal direction. A few MW of heating power is
provided in this way.

3.2. Neutral Beam Heating

Beams of high energy, neutral deuterium or tritium atoms are injected into the plasma,
transferring their energy to the plasma via collisions with the plasma ions. The neutral
beams are produced in two distinct phases. Firstly, a beam of energetic ions is produced

An Introduction to Energy Sources 109

by applying an accelerating voltage of up to 140,000 Volts. However, a beam of charged
ions will not be able to penetrate the confining magnetic field in the tokamak. Thus, the
second stage ensures the accelerated beams are neutralized (i.e. the ions turned into
neutral atoms) before injection into the plasma. In JET, up to 21MW of additional power
is available from the NBI heating systems.

3.3. Radio-Frequency Heating

As the plasma ions and electrons are confined to rotate around the magnetic field lines in
the tokamak, electromagnetic waves of a frequency matched to the ions or electrons are
able to resonate - or damp its wave power into the plasma particles. As energy is
transferred to the plasma at the precise location where the radio waves resonate with the
ion/electron rotation, such wave heating schemes has the advantage of being localized at
a particular location in the plasma.

In JET, eight antennae in the vacuum vessel propagate waves in the frequency range of
25-55 MHz into the core of the plasma. These waves are tuned to resonate with particular
ions in the plasma - thus heating them up. This method can inject up to 20MW of heating
power.

Waves can also be used to drive current in the plasma - by providing a "push" to
electrons traveling in one particular direction. In JET, 10 MW of these so-called Lower
Hybrid microwaves (at 3.7GHz) accelerate the plasma electrons to generate a plasma
current of up to 3 MA.

3.4. Self Heating of Plasma

The Helium ions (or so-called alpha-particles) produced when Deuterium and Tritium
fuse remain within the plasma's magnetic trap for a time - before they are pumped away
through the diverter. The neutrons (being neutral) escape the magnetic field and their
capture in a future fusion power plant will be the source of fusion power to produce
electricity.

The fusion energy contained within the Helium ions heats the D and T fuel ions (by
collisions) to keep the fusion reaction going. When this self heating mechanism is
sufficient to maintain the required plasma temperature for fusion, the reaction becomes
self-sustaining (i.e. no external plasma heating is required). This condition is referred to
as Ignition.

110

Nuclear Fusion

Ohmic
heating

Radio frequency
(RF) Heating

Transmission
lines

Antenna

Neutral beam
injection heating

3.5. Measuring the plasma

Measuring the key plasma properties is one of the most challenging aspects of fusion
research. Knowledge of the important plasma parameters (temperature, density, radiation
losses) is very important in increasing the understanding of plasma behaviour and
designing, with confidence, future devices. However, as the plasma is contained in a
vacuum vessel and its properties are extreme (extremely low density and extremely high
temperature), conventional methods of measurement are not appropriate. Thus, plasma
diagnostics are normally very innovative and often measure a physical process from
which information on a particular parameter can be deduced.

Measurement techniques can be categorized as active or passive. In active plasma
diagnostics, the plasma is probed (via laser beams, microwaves, probes) to see how the
plasma responds. For instance, in interferometers, the passage of a microwave beam
through the plasma will be slow by the presence of the plasma (compared to the passage
through vacuum). This measures the refractive index of the plasma from which the
density of plasma ions/electrons can be interpreted. With all active diagnostics, it must be

An Introduction to Energy Sources

111

ensured that the probing mechanism does not significantly affect the behaviour of the

plasma.

With passive plasma diagnostics, radiation and particles leaving the plasma are measured

- and this knowledge is used to deduce how the plasma behaves under certain conditions.

For instance, during D-T operation on JET, neutron detectors measure the flux of

neutrons emitted form the plasma. All wavelengths of radiated waves (visible, UV waves,

X-rays etc) are also measured - often from many locations in the plasma. Then a detailed

knowledge of the process which created the waves can enable a key plasma parameter to

be deduced.

4. 1. The Hydrogen Bomb: The Basics

A fission bomb, called the primary, produces a flood of radiation including a large

number of neutrons. This radiation impinges on the thermonuclear portion of the bomb,

known as the secondary. The secondary consists largely of lithium deuteride. The

neutrons react with the lithium in this chemical compound, producing tritium and helium.

6 3 Li + 'no -> 4 2 He + 3 iH

The production of tritium from lithium deuteride

This reaction produces the tritium on the spot, so there is no need to include tritium in the
bomb itself. In the extreme heat which exists in the bomb, the tritium fuses with the
deuterium in the lithium deuteride.

The question facing designers was "How do you build a bomb that will maintain the high
temperatures required for thermonuclear reactions to occur?" The shock waves produced
by the primary (A-bomb) would propagate too slowly to permit assembly of the

112

Nuclear Fusion

thermonuclear stage before the bomb blew itself apart. This problem was solved by
Edward Teller and Stanislaw Ulam .

To do this, they introduced a high energy gamma ray absorbing material (styrofoam) to
capture the energy of the radiation. As high energy gamma radiation from the primary is
absorbed, radial compression forces are exerted along the entire cylinder at almost the
same instant. This produces the compression of the lithium deuteride. Additional
neutrons are also produced by various components and reflected towards the lithium
deuteride. With the compressed lithium deuteride core now bombarded with neutrons,
tritium is formed and the fusion process begins.

4.1.1. The Hydrogen Bomb: Schematic

Beryllium neutron
reflector

_ U-238 neutron reflector Fissionable material
and producer

U-238 Tamper — I Styrofoam —

1 — Lithium Deuteride

The yield of a hydrogen bomb is controlled by the amounts of lithium deuteride and of
additional fissionable materials. Uranium 238 is usually the material used in various parts
of the bomb's design to supply additional neutrons for the fusion process. This additional
fissionable material also produces a very high level of radioactive fallout.
4.2. The Neutron Bomb

The neutron bomb is a small hydrogen bomb. The neutron bomb differs from standard
nuclear weapons insofar as its primary lethal effects come from the radiation damage
caused by the neutrons it emits. It is also known as an enhanced-radiation weapon
(ERW).

An Introduction to Energy Sources 113

The augmented radiation effects mean that blast and heat effects are reduced so that

physical structures including houses and industrial installations, are less affected.

Because neutron radiation effects drop off very rapidly with distance, there is a sharper

distinction between areas of high lethality and areas with minimal radiation doses.

5. Advantages of fusion

Fusion offers significant potential advantages as a future source of energy - as just part of

a varied world energy mix.

5.1. Abundant fuels

Deuterium is abundant as it can be extracted from all forms of water. If the entire world's

electricity were to be provided by fusion power stations, present deuterium supplies from

water would last for millions of years.

Tritium does not occur naturally and will be bred from Lithium within the machine.

Therefore, once the reaction is established, even though it occurs between Deuterium and

Tritium, the external fuels required are Deuterium and Lithium.

Lithium is the lightest metallic element and is plentiful in the earth's crust. If all the

world's electricity were to be provided by fusion, known Lithium reserves would last for

at least one thousand years.

The energy gained from a fusion reaction is enormous. To illustrate, 10 grams of

Deuterium (which can be extracted from 500 litres of water) and 15g of Tritium

(produced from 30g of Lithium) reacting in a fusion power plant would produce enough

energy for the lifetime electricity needs of an average person in an industrialized country.

5.2. Inherent safety

The fusion process in a future power station will be inherently safe. As the amount of
Deuterium and Tritium in the plasma at any one time is very small (just a few grams) and
the conditions required for fusion to occur (e.g. plasma temperature and confinement) are
difficult to attain, any deviation away from these conditions will result in a rapid cooling
of the plasma and its termination. There are no circumstances in which the plasma fusion
reaction can 'run away' or proceed into an uncontrollable or critical condition.

5.3. Environmental advantages

Like conventional nuclear (fission) power, fusion power stations will produce no
'greenhouse' gases - and will not contribute to global warming.

114 Nuclear Fusion

As fusion is a nuclear process the fusion power plant structure will become radioactive -
by the action of the energetic fusion neutrons on material surfaces. However, this
activation decays rapidly and the time span before it can be re -used and handled can be
minimized (to around 50 years) by careful selection of low-activation materials. In
addition, unlike fission, there is no radioactive 'waste' product from the fusion reaction
itself. The fusion byproduct is Helium - an inert and harmless gas.
References

1 . Essentials of Nuclear Chemistry, H. J. Arnikar, Fourth Edition, New Age
International (P) Limited, Publishers, 1995.

2. Chemistry of Nuclear Power, J. K. Dawson and G. Long.

3. Nuclear Energy, Raymond I Murry.

4. http://hvperphvsics.phv-astr.gsu.edu/HBASE/nucene/fusion.htm/

5. http://fusedweb.pppl.gov

Chapter - 7

BATTERIES - FUNDAMENTALS
M. Helen

1. Introduction

Batteries are all over the place -- in our cars, our PCs, laptops, portable MP3 players and cell
phones. A battery is essentially a can full of chemicals that produce electrons. Chemical
reactions that produce electrons are called electrochemical reactions. The basic concept
at work, the actual chemistry going on inside a battery and what the future holds for
batteries are the scope of this chapter.

•

2n 2 +

-e--

Zn
t

e -

Cu«*

Zn ^

sqf"

2 +

ZnSOi, solution CuSOi solution

electrolyte j electrolyte

Anode

Separate

Electrolyte Cathode

separator

Fig 1. Representation of a battery (Daniel cell) showing the key features of battery
operation

If you look at any battery, you will notice that it has two terminals. One terminal is marked
(+), or positive is cathode, while the other is marked (-), or negative is the anode. The
anode is the negative electrode of a cell associated with oxidative chemical reactions that
release electrons into the external circuit. The cathode is the positive electrode of a cell
associated with reductive chemical reactions that gain electrons from the external circuit.
We also have active mass, material that generates electrical current by means of a

116

Batteries - Fundamentals

chemical reaction within the battery. An electrolyte is a material that provides pure
ionic conductivity between the positive and negative electrodes of a cell and a separator
is a physical barrier between the positive and negative electrodes incorporated into most
cell designs to prevent electrical shorting. The separator can be a gelled electrolyte or a
microporous plastic film or other porous inert material filled with electrolyte.
Separators must be permeable to the ions and inert in the battery environment.
2. Battery Operation

The negative electrode is a good reducing agent (electron donor) such as lithium, zinc, or
lead. The positive electrode is an electron acceptor such as lithium cobalt oxide,
manganese dioxide, or lead oxide. The electrolyte is a pure ionic conductor that
physically separates the anode from the cathode. In practice, a porous electrically
insulating material containing the electrolyte is often placed between the anode and
cathode to prevent the anode from directly contacting the cathode. Should the anode
and cathode physically touch, the battery will be shorted and its full energy released as
heat inside the battery. Electrical conduction in electrolytic solutions follows Ohm's
law: E = IR

Two dissimilar metals placed in an acid bath produce electrical potential across the poles.
The cell produces voltage by a chemical reaction between the plates and the electrolyte.
The positive plate is made of reddish-brown material such as lead dioxide (Pb02) while
the negative plate is made of grayish material called sponge lead (Pb). The acid bath is a
mixture of sulfuric acid and water giving the cell electrolyte. Together a cell element is
formed as shown in Fig.2.

Anode ^el Cathode

— <> —

Charging

PbO,

Electrolyte
Water + acid

Discharging

Fig 2. Representation of a lead acid battery

Energy Sources - A Chemist's Perspective 117

3. Cycling

The battery stores electricity in the form of chemical energy. Through a chemical
reaction process, the battery creates and releases electricity as needed by the electrical
system or devices. Since the battery loses its chemical energy in this process, the battery
must be recharged by the alternator. By reversing electrical current flow through the
battery the chemical process is reversed, thus charging the battery. The cycle of
discharging and charging is repeated continuously and is called "battery cycling".

4. History of Batteries

The first battery was created by Alessandro Volta in 1800. To create his battery, he made a
stack by alternating layers of zinc, blotting paper soaked in salt water, and silver. This
arrangement was known as a voltaic pile. The top and bottom layers of the pile must be
different metals, as shown in Fig. 3. If one attaches a wire to the top and bottom of the

pile, one can measure a voltage and a current from the pile.

I////////// I

V/////////

\//////////

□H] Zinc
7771 Silver
IZZ1 Blotter

Fig. 3. Zinc-silver voltaic pile
In the 1800s, before the invention of the electrical generator, the Daniel cell (which is also
known by three other names -- the "Crowfoot cell" because of the typical shape of the zinc
electrode, the "gravity cell" because gravity keeps the two sulfates separated, and a "wet
cell," as opposed to the modern "dry cell," because it uses liquids for the electrolytes), was
common for operating telegraphs and doorbells. The Daniel cell is a wet cell consisting of
copper and zinc plates and copper and zinc sulphates. The Plante lead acid battery was
introduced in 1859 and Leclanche introduced in 1869 the forerunner of today's dry cell.
The first true dry cell was developed in 1881 by Gassner and commercial production of the
cell was then started. The other important dates in the history of the battery are: 1900- the
Edison nickel storage battery, 1943-the Adams copper chlorine battery, 1945-the mercury
cell, and 1955- the alkaline manganese dioxide dry cell. Developments continue to meet

118 Batteries - Fundamentals

the requirements of current technology. Lithium batteries are commonly used in many
devices and sodium sulphur battery has been developed for automobiles.

5. Classification of batteries

Batteries can either be a primary cell, such as a flashlight battery once used, throw it
away, or a secondary cell, such as a car battery (when the charge is gone, it can be
recharged).

Primary cell: Because the chemical reaction totally destroys one of the metals after a
period of time, primary cells cannot be recharged. Small batteries such as flashlight and
radio batteries are primary cells.

Secondary cell: The metal plates and acid mixture change as the battery delivers current.
As the battery drains the metal plates become similar and the acid strength weakens. This
process is called discharging. By applying current to the battery in the reverse direction,
the battery materials can be restored, thus recharging the battery. This process is called
charging. Automotive lead-acid batteries are secondary cells and can be recharged.
These batteries are also classified as wet or dry charged batteries. Batteries can be
produced as Wet-Charged, such as current automotive batteries are today, or they can be
Dry-Charged, such as a motorcycle battery where an electrolyte solution is added when
put into service.

• WET-CHARGED: The lead- acid battery is filled with electrolyte and charged
when it is built. Periodic charging is required. Most batteries sold today are wet
charged.

• DRY-CHARGED: The battery is built, charged, washed and dried, sealed, and
shipped without electrolyte. It can be stored for up to 18 months. When put into
use, electrolyte and charging are required. Batteries of this type have a long shelf
life. Motorcycle batteries are typically dry charged batteries.

6. Primary batteries

6.1. Leclanche Cells (zinc carbon or dry cell)

The basic design of the Leclanche cell has been around since the 1860s, and until World
War II, was the only one in wide use. It is still the most commonly used of all primary
battery designs because of its low cost, availability, and applicability in various
situations. However, because the Leclanche cell must be discharged intermittently for

Energy Sources - A Chemist's Perspective 119

best capacity, much of battery research in the last three decades has focused on zinc-
chloride cell systems, which have been found to perform better than the Leclanche under
heavier drain.

Anode: Zinc

Cathode: Manganese Dioxide (Mn0 2 )

Electrolyte: Ammonium chloride or zinc chloride dissolved in water

Applications: Flashlights, toys, moderate drain use
In an ordinary Leclanche cell the electrolyte consists (in percent of atomic weight) of
26% NH4CI (ammonium chloride), 8.8% ZnCl 2 (zinc chloride), and 65.2% water. The
overall cell reaction can be expressed:

Zn + 2Mn0 2 +2NH 4 C1 — > 2MnOOH + Zn(NH 3 ) 2 Cl 2 E = 1 .26

The electrolyte in a typical zinc chloride cell consists of 15-40% ZnCl 2 and 60-85%
water, sometimes with a small amount of NH4CI for optimal performance. The overall
cell reaction of the zinc chloride as the electrolyte can be expressed:
Zn + 2Mn0 2 + 2H 2 + ZnCl 2 — > 2MnOOH + 2 Zn(OH)Cl

Mn0 2 , is only slightly conductive, so graphite is added to improve conductivity. The cell
voltage increases by using synthetically produced manganese dioxide instead of that
found naturally (called pyrolusite). This does drive the cost up a bit, but it is still
inexpensive and environmentally friendly, making it a popular cathode.
These cells are the cheapest ones in wide use, but they also have the lowest energy
density and perform poorly under high-current applications. Still, the zinc carbon design
is reliable and more than adequate for many everyday applications.
6.2. Alkaline Cells

This cell design gets its name from the use of alkaline aqueous solutions as electrolytes.
Alkaline battery chemistry was first introduced in the early 1960s. The alkaline cell has
grown in popularity, becoming the zinc-carbon cell's greatest competitor. Alkaline cells
have many acknowledged advantages over zinc-carbon, including a higher energy
density, longer shelf life, superior leakage resistance, better performance in both
continuous and intermittent duty cycles, and lower internal resistance, which allows it to
operate at high discharge rates over a wider temperature range.

Anode: Zinc powder

120 Batteries - Fundamentals

Cathode: Manganese dioxide (Mn0 2 ) powder

Electrolyte: Potassium hydroxide (KOH)

Applications: Radios, toys, photo-flash applications, watches, high-drain

applications
Zinc in powdered form increases the surface area of the anode, allowing more particle-
particle interaction. This lowers the internal resistance and increases the power density.
The cathode, MnC>2, is synthetically produced because of its superiority to naturally
occurring MnC>2. This increases the energy density. Just as in the zinc carbon cell,
graphite is added to the cathode to increase conductivity. The electrolyte, KOH, allows
high ionic conductivity. Zinc oxide is often added to slow down corrosion of the zinc
anode. A cellulose derivative is thrown in as a gelling agent. These materials make the
alkaline cell more expensive than the zinc-carbon, but its improved performance makes it
more cost effective, especially in high drain situations where the alkaline cell's energy
density is higher.
The half-reactions are:
Zn + 2 OH" — > ZnO + H 2 + 2 e"
2 Mn0 2 + H 2 + 2 e" — >Mn 2 3 + 2 OH"
The overall reaction is:
Zn + 2Mn0 2 — > ZnO + Mn 2 3 E = 1 .5 V

There are other cell designs that fit into the alkaline cell category, including the mercury
oxide, silver oxide, and zinc air cells. Mercury and silver give even higher energy
densities, but cost a lot more and are being phased out through government regulations
because of their high heavy metal toxicity. The mercury oxide, silver oxide, and zinc air
(which are being developed for electronic vehicles) are considered separately.
6.3. Mercury Oxide Cells

This is an obsolete technology. Most if not all of the manufacture of these cells has been
stopped by government regulators. Mercury batteries come in two main varieties:
zinc/mercuric oxide and cadmium/mercuric oxide. The zinc/mercuric oxide system has
high volumetric specific energy (400 Wh/L), long storage life, and stable voltage. The
cadmium/mercuric oxide system has good high temperature and good low temperature (-
55 °C to +80°C, some designs to +180°C) operation and has very low gas evolution.

Energy Sources - A Chemist's Perspective 121

Anode: Zinc (or cadmium)

Cathode: Mercuric Oxide (HgO)

Electrolyte: Potassium hydroxide

Applications: Small electronic equipment, hearing aids, photography, alarm

systems, emergency beacons, detonators, radio microphones
Basic cell reaction:
Zn + HgO = ZnO + Hg E = 1.35 V
Cd + HgO + H 2 = Cd(OH 2 ) + Hg E = 0.91 V

The electrolytes used in mercury cells are sodium and/or potassium hydroxide solutions,
making these alkaline cells. These cells are not rechargeable.
6.4. Zinc/ Air Cells

The zinc air cell fits into the alkaline cell category because of its electrolyte. It also acts
as a partial fuel cell because it uses the 2 from air as the cathode. This cell is an
interesting technology, even aside from the question "how do you use air for an
electrode?" Actually, oxygen is let in to the cathode through a hole in the battery and is
reduced on a carbon surface.

Anode: Amalgamated zinc powder and electrolyte

Cathode: Oxygen (0 2 )

Electrolyte: Potassium hydroxide (KOH)

Applications: Hearing aids, pagers, electric vehicles
A number of battery chemistries are involved in a metal oxide and zinc. The metal oxide
reduces, the zinc becomes oxidized, and electric current results. A familiar example is the
old mercury oxide/zinc batteries used for hearing aids. If you leave out the metal oxide
you could double the capacity per unit volume (roughly), but where would you get the
oxygen?

The half-reactions are:
Zn 2+ + 20H" — > Zn(OH) 2
1/2 2 + H 2 + 2e — > 2 OH"
The overall reaction is:
2Zn +0 2 +2H 2 — > 2Zn(OH) 2 E = 1.65 V

122 Batteries - Fundamentals

The electrolyte is an alkali hydroxide in 20-40% weight solution with water. One
disadvantage is that since these hydroxides are hygroscopic, they will pick up or lose
water from the air depending on the humidity. Both too little and too much humidity
reduces the life of the cell. Selective membranes can help. Oxygen from air dissolves in
the electrolyte through a porous, hydrophobic electrode — a carbon-polymer or metal-
polymer composite.

The energy density of these batteries can be quite high, between 220-300 Wh/kg
(compared to 99-123 Wh/kg with an HgO cathode), although the power density remains
low. However, the use of potassium or sodium hydroxides as the electrolyte is a
problem, since these can react with carbon dioxide in the air to form alkali carbonates.
For this reason large zinc air batteries usually contain a higher volume of CO2 absorbing
material (calcium oxide flake) than battery components. This can cancel out the huge
increase in energy density gained by using the air electrode.

This cell has the additional benefits of being environmentally friendly at a relatively low
cost. These batteries can last indefinitely before they are activated by exposing them to
air, after which they have a short shelf life. For this reason (as well as the high energy
density) most zinc-air batteries are used in hearing aids.
6.5. Aluminum / Air Cells

Although, to our way of thinking, the metal/air batteries are strictly primary, cells have
been designed to have the metal replaceable. These are called mechanically rechargeable
batteries. Aluminum/air is an example of such a cell. Aluminum is attractive for such
cells because it is highly reactive, the aluminum oxide protective layer is dissolved by
hydroxide electrolytes, and it has a high voltage.
Half cell reactions are:
Al + 4 OH"— > Al(OH) 4 " + 3e
3/4 2 + 3/2 H 2 + 3e— > 30H"
The overall reaction is

Al + 3/2 HO + 3/4 2 — > Al (OH) 3 E = 2.75 V

As mentioned above, alkali (chiefly potassium hydroxide) electrolytes are used, but so
also are neutral salt solutions. The alkali cell has some problem with the air electrode,
because the hydroxide ion makes a gel in the porous electrode, polarizing it. The typical

Energy Sources - A Chemist's Perspective 123

aluminum hydroxide gel is a problem on either electrode because it sucks up a lot of
water. Using a concentrated caustic solution prevents this, but is very reactive with the
aluminum electrode, producing hydrogen gas. Another way to prevent the gel formation
is to seed the electrolyte with aluminum trihydroxide crystals. These act to convert the
aluminum hydroxide to aluminum trihydroxide crystals and they grow. To prevent
hydrogen gas evolution tin and zinc have been used as corrosion inhibitors. A number of
additives are used to control the reactions. A disadvantage of the alkaline electrolyte is
that it reacts with atmospheric carbon dioxide.

Aluminum / air cells have also been made for marine applications. These are
"rechargeable" by replacing the sea water electrolyte until the aluminum is exhausted,
then replacing the aluminum. Some cells that are open to sea water have also been
researched. Since salt water solutions tend to passivate the aluminum, pumping the
electrolyte back and forth along the cell surface has been successful. For those cells that
do not need to use ocean water, an electrolyte of KC1 and KF solutions is used.
Air electrodes of Teflon-bonded carbon are used without a catalyst.
6.6. Lithium Cells

Chemistry of lithium battery comprises a number of cell designs that use lithium as the
anode. Lithium is gaining a lot of popularity as an anode for a number of reasons. Note
that lithium, the lightest of the metals, also has the highest standard potential of all the
metals, at over 3 V. Some of the lithium cell designs have a voltage of nearly 4 V. This
means that lithium has the highest energy density. Many different lithium cells exist
because of its stability and low reactivity with a number of cathodes and non-aqueous
electrolytes. The most common electrolytes are organic liquids with the notable
exceptions of SOCL (thionyl chloride) and SO2CI2 (sulfuryl chloride). Solutes are added
to the electrolytes to increase conductivity.

Lithium cells have only recently become commercially viable because lithium reacts
violently with water, as well as nitrogen in air. This requires sealed cells. High-rate
lithium cells can build up pressure if they short circuit and cause the temperature and
pressure to rise. Thus, the cell design needs to include weak points, or safety vents, which
rupture at a certain pressure to prevent explosion.

124 Batteries - Fundamentals

Lithium cells can be grouped into three general categories: liquid cathode, solid cathode,
and solid electrolyte. Let's look at some specific lithium cell designs within the context of
these three categories
6.6.1. Liquid cathode lithium cells

These cells tend to offer higher discharge rates because the reactions occur at the cathode
surface. In a solid cathode, the reactions take longer because the lithium ions must enter
into the cathode for discharge to occur. The direct contact between the liquid cathode and
the lithium forms a film over the lithium, called the solid electrolyte interface (SEI). This
prevents further chemical reaction when not in use, thus preserving the cell's shelf life.
One drawback, though, is that if the film is too thick, it causes an initial voltage delay.
Usually, water contamination is the reason for the thicker film, so quality control is
important.

• LiS0 2 Lithium-Sulfur Dioxide

This cell performs well in high current applications as well as in low temperatures. It has

an open circuit voltage of almost 3 V and a typical energy density of 240-280 Wh/kg. It

uses a cathode of porous carbon with sulfur dioxide taking part in the reaction at the

cathode. The electrolyte consists of an acetonitrile solvent and a lithium bromide solute.

Polypropylene acts as a separator. Lithium and sulfur dioxide combine to form lithium

dithionite:

2Li + 2S0 2 — > Li 2 S 2 4

These cells are mainly used in military applications for communication because of high

cost and safety concerns in high-discharge situations, i.e., pressure buildup and

overheating.

• LiSOCl 2 Lithium Thionyl Chloride

This cell consists of a high-surface area carbon cathode, a non- woven glass separator,
and thionyl chloride, which doubles as the electrolyte solvent and the active cathode
material. Lithium aluminum chloride (L1AICI4) acts as the electrolyte salt.

The materials react as follows:

Li — > Li + + e"

4Li + + 4e" + 2S0C1 2 — > 4LiCl + S0 2 + S

overall reaction:

Energy Sources - A Chemist's Perspective 125

4Li + 2S0C1 2 — > 4LiCl + S0 2 + S

During discharge the anode gives off lithium ions. On the carbon surface, the thionyl

chloride reduces to chloride ions, sulfur dioxide, and sulfur. The lithium and chloride ions

then form lithium chloride. Once the lithium chloride has deposited at a site on the carbon

surface, that site is rendered inactive. The sulfur and sulfur dioxide dissolve in the

electrolyte, but at higher-rate discharges SO2 will increase the cell pressure.

This system has a very high energy density (about 500 Wh/kg) and an operating voltage

of 3.3-3.5 V. The cell is generally a low-pressure system

In high-rate discharge, the voltage delay is more pronounced and the pressure increases

as mentioned before. Low-rate cells are used commercially for small electronics and

memory backup. High-rate cells are used mainly for military applications.

6.6.2. Solid cathode lithium cells

These cells cannot be used in high-drain applications and do not perform as well as the

liquid cathode cells in low temperatures. However, they do not have the same voltage

delay and the cells do not require pressurization. They are used generally for memory

backup, watches and portable electronic devices.

• LiMn0 2

These accounts for about 80% of all primary lithium cells, one reason being their low

cost. The cathode used is a heat-treated Mn02 and the electrolyte is a mixture of

propylene carbonate and 1,2-dimethoyethane. The half reactions are

Li — > Li + + e-

Mn w 2 + Li + + e — > Mn m 2 (Li + )

Overall reaction:

Li + Mn IV 2 — > Mn m 2 (Li + )

At lower temperatures and in high-rate discharge, the LiS0 2 cell performs better than the

LiMn0 2 cell. At low-rate discharge and higher temperatures, the two cells perform

equally well, but LiMn0 2 cell has the advantage because it does not require

pressurization.

• Li(CF) n Lithium polycarbon mono fluoride

The cathode in this cell is carbon monofluoride, a compound formed through high-
temperature intercalation. This is the process where foreign atoms (in this case fluorine

126 Batteries - Fundamentals

gas) are incorporated into some crystal lattice (graphite powder), with the atoms of the

crystal lattice retaining their positions relative to one another.

A typical electrolyte is lithium tetrafluorobate (L1BF4) salt in a solution of propylene

carbonate (PC) and dimethoxyethane (DME)

These cells also have a high voltage (about 3.0 V open voltage) and a high energy density

(around 250 Wh/kg). All this and a 7-year shelf life make them suitable for low- to

moderate-drain use, e.g., watches, calculators, and memory applications.

6.6.3. Solid electrolyte lithium cells

All commercially manufactured cells that use a solid electrolyte have a lithium anode.

They perform best in low-current applications and have a very long service life. For this

reason, they are used in pacemakers

• LH2 — Lithium iodine cells use solid Lil as their electrolyte and also produce Lil

as the cell discharges. The cathode is poly-2-vinylpyridine (P2VP) with the

following reactions:
2Li — > 2Li + + 2e

2Li + + 2e + P2VP- nl 2 — > P2VP- (n-l)I 2 + 2LiI
2Li + P2VP- nl 2 — > P2VP- (n-l)I 2 +2LiI
Lil is formed in situ by direct reaction of the electrodes.
6.7. Lithium-Iron Cells

The Lithium-Iron chemistry deserves a separate section because it is one of a handful of
lithium metal systems that have a 1.5 volt output (others are lithium/lead bismuthate,
lithium/bismuth trioxide, lithium/copper oxide, and lithium/copper sulfide). Recently
consumer cells that use the Li/Fe have reached the market, including the Energizer. These
have the advantage of having the same voltage as alkaline batteries with more energy
storage capacity, so they are called "voltage compatible" lithium cells. They are not
rechargeable. They have about 2.5 times the capacity of an alkaline battery of the same
size, but only under high current discharge conditions (digital cameras, flashlights, motor
driven toys, etc.). For small currents they do not have any advantage. Another advantage
is the low self-discharge rate-10 year storage is quoted by the manufacturer. The
discharge reactions are:
2 FeS 2 + 4 Li — > Fe + 2Li 2 S 1 .6 Volts

Energy Sources - A Chemist's Perspective 127

FeS + 2Li — > Fe + Li 2 S 1.5 Volts

Both Iron sulfide and Iron disulfide are used, the FeS2 is used in the Energizer.

Electrolytes are organic materials such as propylene carbonate, dioxolane and

dimethoxy ethane .

6.8. Magnesium-Copper Chloride Reserve Cells

The magnesium-cuprous chloride system is a member of the reserve cell family. It can't

be used as a primary battery because of its high self-discharge rate, but it has a high

discharge rate and power density, so it can be made "dry charged" and sit forever ready,

just add water. The added advantage of being light-weight has made these practical for

portable emergency batteries. It works by depositing copper metal out onto the

magnesium anode, just like the old copper-coated nail experiment. Variations of this

battery use silver chloride, lead chloride, copper iodide, or copper thiocyanate to react

with the magnesium. The torpedo batteries force seawater through the battery to get up

to 460 kW of power to drive the propeller.

Mg + 2 CuCl — > MgCl 2 + 2 Cu E = 1 .6 Volts

7. Secondary Batteries

7.1. Lead-acid Cells

Anode: Sponge metallic lead

Cathode: Lead dioxide (PbCh)

Electrolyte: Dilute mixture of aqueous sulfuric acid

Applications: Motive power in cars, trucks, forklifts, construction equipment,

recreational water craft, standby/backup systems
Used mainly for engine batteries, these cells represent over half of all battery sales. Some
advantages are their low cost, long life cycle, and ability to withstand mistreatment. They
also perform well in high and low temperatures and in high-drain applications. The
chemistry of lead acid battery in terms of half-cell reactions are:
Pb + S0 4 2 " — > PbS0 4 + 2e"
Pb0 2 + S0 4 2 " + 4H + + 2e" — > PbS0 4 + 2H 2

There are a few problems with this design. If the cell voltages exceed 2.39 V, the water
breaks down into hydrogen and oxygen (this so-called gassing voltage is temperature
dependent). This requires replacing the cell's water. Also, as the hydrogen and oxygen

128 Batteries - Fundamentals

vent from the cell, too high a concentration of this mixture will cause an explosion.
Another problem arising from this system is that fumes from the acid or hydroxide
solution may have a corrosive effect on the area surrounding the battery.
These problems are mostly solved by sealed cells, made commercially available in the
1970s. In the case of lead acid cells, the term "valve-regulated cells" is more accurate,
because they cannot be sealed completely. If they were, the hydrogen gas would cause
the pressure to build up beyond safe limits. Catalytic gas recombination does a great deal
to alleviate this problem. They convert the hydrogen and oxygen back into water,
achieving about 85% efficiency at best. Although this does not entirely eliminate the
hydrogen and oxygen gas, the water lost becomes so insignificant that no refill is needed
for the life of the battery. For this reason, these cells are often referred to as maintenance-
free batteries. Also, this cell design prevents corrosive fumes from escaping.
These cells have a low cycle life, a quick self discharge, and low energy densities
(normally between 30 and 40 Wh/kg). However, with a nominal voltage of 2 V and
power densities of up to 600 W/kg, the lead-acid cell is an adequate, if not perfect, design
for car batteries.
7.2. Nickel/Cadmium Cells

Anode: Cadmium

Cathode: Nickel oxyhydroxide Ni(OFf)2

Electrolyte: Aqueous potassium hydroxide (KOH)

Applications: Calculators, digital cameras, pagers, lap tops, tape recorders,

flashlights, medical devices (e.g., defibrillators), electric vehicles, space

applications
The cathode is nickel-plated, woven mesh, and the anode is a cadmium-plated net. Since
the cadmium is just a coating, this cell's negative environmental impact is often
exaggerated. (Incidentally, cadmium is also used in TV tubes, some semiconductors, and
as an orange-yellow dye for plastics.) The electrolyte, KOH, acts only as an ion
conductor and does not contribute significantly to the cell's reaction. That's why not much
electrolyte is needed, so this keeps the weight down. (NaOH is sometimes used as an
electrolyte, which does not conduct as well, but also does not tend to leak out of the seal
as much). Here are the cell reactions:

Energy Sources - A Chemist's Perspective 129

Cd + 20H" — > Cd(OH) 2 + 2e"
Ni0 2 + 2H 2 + 2e" — > Ni(OH) 2 + 20H"
Overall reaction:

Cd +Ni0 2 + 2H 2 — > Cd(OH) 2 + Ni(OH) 2

Advantages include good performance in high-discharge and low-temperature
applications. They also have long shelf and use life. Disadvantages are that they cost
more than the lead-acid battery and have lower power densities. Possibly the most well-
known limitation is a memory effect, where the cell retains the characteristics of the
previous cycle.

This term refers to a temporary loss of cell capacity, which occurs when a cell is
recharged without being fully discharged. This can cause cadmium hydroxide to
passivate the electrode, or the battery to wear out. In the former case, a few cycles of
discharging and charging the cell will help correct the problem, but may shorten the life
time of the battery. The true memory effect comes from the experience with a certain
style of Ni-Cd in space use, which was cycled within a few percent of discharge each
time.

An important thing to know about "conditioning" a Ni-Cd battery is that the deep
discharge.
7.3. Nickel/Metal Hydride (NiMH) Cells

Anode: Rare-earth or nickel alloys with many metals

Cathode: Nickel oxyhydroxide

Electrolyte: Potassium hydroxide

Applications: Cellular phones, camcorders, emergency backup lighting, power

tools, laptops, portable, electric vehicles
This sealed cell is a hybrid of the NiCd and NiH 2 cells. Previously, this battery was not
available for commercial use because, although hydrogen has wonderful anodic qualities,
it requires cell pressurization. Fortunately, in the late 1960s scientists discovered that
some metal alloys (hydrides such as L1M5 or ZrNi 2 ) could store hydrogen atoms, which
then could participate in reversible chemical reactions. In modern NiMH batteries, the
anode consists of many metals alloys, including V, Ti, Zr, Ni, Cr, Co, and Fe.

130 Batteries - Fundamentals

Except for the anode, the NiMH cell very closely resembles the NiCd cell in construction.

Even the voltage is virtually identical, at 1.2 volts, making the cells interchangeable in

many applications. The cell reactions are:

MH + OH" — > M + H 2 + e"

NiOOH + H 2 + e" — > Ni(OH) 2 + OH"

Over all reaction:

NiOOH + MH — > Ni(OH) 2 + M E = 1 .35 V

The anodes used in these cells are complex alloys containing many metals, such as an

alloy of V, Ti, Zr, Ni, Cr, Co and Fe. The underlying chemistry of these alloys and

reasons for superior performance are not clearly understood, and the compositions are

determined by empirical testing methods.

A very interesting fact about these alloys is that some metals absorb heat when absorbing

hydrogen, and some give off heat when absorbing hydrogen. Both of these are bad for a

battery, since one would like the hydrogen to move easily in and out without any energy

transfer. The successful alloys are all mixtures of exothermic and endothermic metals to

achieve this. The electrolyte of commercial NiMH batteries is typically 6 M KOH

The NiMH cell does cost more and has half the service life of the NiCd cell, but it also

has 30% more capacity, increased power density (theoretically 50% more, practically

25% more). The memory effect, which was at one time thought to be absent from NiMH

cells, is present if the cells are treated just right. To avoid the memory effect, fully

discharge once every 30 or so cycles. There is no clear winner between the two. The

better battery depends on what characteristics are crucial for a specific application.

7.4. Lithium Ion Cells

Anode: Carbon compound, graphite

Cathode: Lithium oxide

Electrolyte:

Applications: Laptops, cellular phones, electric vehicles
Lithium batteries that use lithium metal have safety disadvantages when used as
secondary (rechargeable) energy sources. For this reason a series of cell chemistries have
been developed using lithium compounds instead of lithium metal. These are called
generically Lithium ion Batteries.

Energy Sources - A Chemist's Perspective 131

Cathodes consist of a layered crystal (graphite) into which the lithium is intercalated.
Experimental cells have also used lithiated metal oxide such as LiCoC>2, NiNio.3Coo.7O2,
LiNi0 2 , L1V2O5, LiVeOn, L1M114O9, LiMn 2 4 , LiNiOo. 2 Co0 2 .

Electrolytes are usually LiPF 6 , although this has a problem with aluminum corrosion, and
so alternatives are being sought. One such is L1BF4. The electrolyte in current production
batteries is liquid, and uses an organic solvent.

Membranes are necessary to separate the electrons from the ions. Currently the batteries
in wide use have microporous polyethylene membranes.

Intercalation (rhymes with relation — not inter-cal, but in-tercal-ation) is a long-studied
process which has finally found a practical use. It has long been known that small ions
(such as lithium, sodium, and the other alkali metals) can fit in the interstitial spaces in a
graphite crystal. Not only that, but these metallic atoms can go farther and force the
graphitic planes apart to fit two, three, or more layers of metallic atoms between the
carbon sheets. You can imagine what a great way this is to store lithium in a battery — the
graphite is conductive, dilutes the lithium for safety, is reasonably cheap, and does not
allow dendrites or other unwanted crystal structures to form.

7.5. Manganese- Titanium (Lithium) Cells
Anode: Lithium-Titanium Oxide

Cathode: Lithium intercalated Manganese Dioxide

Electrolyte:

Applications: Watches, other ultra-low discharge applications

This technology might be called Manganese-Titanium, but it is just another lithium coin

cell. It has "compatible" voltage - 1.5 V to 1.2 Volts, like the Lithium-Iron cell, which

makes it convenient for applications that formerly used primary coin cells. It is unusual

for a lithium based cell because it can withstand a continuous overcharge at 1.6 to 2.6

volts without damage. Although rated for 500 full discharge cycles, it only has a 10% a

year self-discharge rate, and so is used in solar charged watches with expected life of 15+

years with shallow discharging. The amp-hour capacity and available current output of

these cells is extremely meager. The range of capacities from Panasonic is 0.9 to 14

mAH. The maximum continuous drain current is 0.1 to 0.5 mA.

7.6. Rechargeable Alkaline Manganese Cells

132 Batteries - Fundamentals

Anode: Zinc

Cathode: Manganese dioxide

Electrolyte: Potassium Hydroxide Solution

Applications: Consumer devices

This is the familiar alkaline battery, specially designed to be rechargeable, and with a hot

new acronym — RAM. In the charging process, direct-current electrical power is used to

reform the active chemicals of the battery system to their high-energy charge state. In

the case of the RAM battery, this involves oxidation of manganese oxyhydroxide

(MnOOH) in the discharged positive electrode to manganese dioxide (MnC^), and of zinc

oxide (ZnO) in the negative electrode to metallic zinc.

Care must be taken not to overcharge to prevent electrolysis of the KOH solution

electrolyte, or to charge at voltages higher than 1.65 V (depending on temperature) to

avoid the formation of higher oxides of manganese.

7.7. Redox (Liquid Electrode) Cells

These consist of a semi-permeable membrane having different liquids on either side. The

membrane permits ion flow but prevents mixing of the liquids. Electrical contact is

made through inert conductors in the liquids. As the ions flow across the membrane an

electric current is induced in the conductors. These cells and batteries have two ways of

recharging. The first is the traditional way of running current backwards. The other is

replacing the liquids, which can be recharged in another cell. A small cell can also be

used to charge a great quantity of liquid, which is stored outside the cells. This is an

interesting way to store energy for alternative energy sources that are unreliable, such as

solar, wind, and tide. These batteries have low volumetric efficiency, but are reliable and

very long lived.

Electrochemical systems that can be used are FeCl3 (cathode) and TiCi3 or CrCb (anode).

Vanadium redox cells: A particularly interesting cell uses vanadium oxides of different

oxidation states as the anode and cathode. These solutions will not be spoiled if the

membrane leaks, since the mixture can be charged as either reducing or oxidizing

components.

Energy Sources - A Chemist's Perspective 133

8. Selection criteria for Battery Systems

A set of criteria that illustrate the characteristics of the materials and reactions for a
commercial battery system are:

/. Mechanical and Chemical Stability: The materials must maintain their mechanical
properties and their chemical structure and composition over the course of time and
temperature as much as possible. Mechanical and chemical stability limitations arise
from reaction with the electrolyte, irreversible phase changes and corrosion, isolation of
active materials, and poor conductivity of materials in the discharged state, etc.

2. Energy Storage Capability: The reactants must have sufficient energy content to
provide a useful voltage and current level, measured in Wh/L or Wh/kg. In addition, the
reactants must be capable of delivering useful rates of electricity, measured in terms of
W/L or W/kg. This implies that the kinetics of the cell reaction are fast and without
significant kinetics hindrances. The carbon-zinc and Ni-Cd systems set the lower limit
of storage and release capability for primary and rechargeable batteries, respectively.

3. Temperature Range of Operation: For military applications, the operational
temperature range is from -50 to 85 °C. Essentially the same temperature range applies
to automotive applications. For a general purpose consumer battery, the operating
temperature range is 0-40 °C, and the storage temperatures range from -20 to 85 °C.
These temperatures are encountered when using automobiles and hand-held devices in
the winter in northern areas and in the hot summer sun in southern areas.

4. Self-Discharge: Self-discharge is the loss of performance when a battery is not in use.
An acceptable rate of loss of energy in a battery depends somewhat on the application
and the chemistry of the system. People expect a battery to perform its intended task on
demand. Li-MnC^ primary cells will deliver 90% of their energy even after 8 years on
the shelf; that is, their self-discharge is low. Some military batteries have a 20-year
storage life and still deliver their rated capacity.

5. Cost: The cost of the battery is determined by the materials used in its fabrication and
the manufacturing process. The manufacturer must be able to make a profit on the sale to
the customer. The selling price must be in keeping with its perceived value (tradeoff of
the ability of the user to pay the price and the performance of the battery).

134 Batteries - Fundamentals

6. Safety: All consumer and commercial batteries must be safe in the normal operating
environment and not present any hazard under mild abuse conditions. The cell or battery
should not leak, vent hazardous materials, or explode.
References

1. R. Narayan and B. Viswanathan. 'Chemical and electrochemical energy systems',
University Press (India) Ltd, 1998.

2. www.duracell.com/OEM

3. data.energizer.com

4. www.powerstream.com

5. M. Winter, R. J . Brodd, Chem. Rev. 104 (2004) 4245-4269.

Chapter - 8

SOLID STATE BATTERIES
L. Hima Kumar
1. Introduction

A force is something that pushes against something else such as gravity. Should it
succeed, work gets done. If a one pound weight is lifted one foot, then one foot-pound of
work has been done on the weight itself. Both force and distance are needed before work
gets done. Energy is just the capacity to do work or the ability to employ a force that
moves something through a distance or performs some exact electrical, thermal,
chemical, or whatever equivalent to mechanical work. Power is the time rate of doing
work. Thus, energy is "how much" and power is "how fast". An energy source is a
substance or a system that can be capable of delivering net kilowatt hours of energy.
An energy carrier is some means of moving energy from one location to another.
Batteries, flywheels, utility pumped storage and terrestrial hydrogen are examples. They
are carriers or "energy transfer systems" because you first have to "fill" them with energy
before you can "empty" them. Without fail, all energy carriers consume significantly
more existing old energy than they can return as new.

Batteries are devices which convert chemical energy into electrical energy.
Thermodynamically, an electrochemical e.m.f system (a so-called battery) is generated if
an electrolyte is sandwiched between two electrode materials with different chemical
potentials. Further, if a constant supply of ions can be maintained and transported through
the electrolyte, it will deliver current when connected across a load resistance. Two
different kinds of batteries are used, primary and secondary; they comprise liquid or solid
electrodes and electrolytes. Primary batteries are batteries designed to be used for one
discharge cycle (non-rechargeable) and then discarded. Secondary batteries are designed
to be recharged and re-used many times and are better known as rechargeable batteries.
Batteries can also be classified by the type of electrolyte which they contain. The
electrolyte can either be liquid (wet cell batteries) or paste-like/gel-like (dry cell
batteries).

136 Solid State Batteries

All batteries operate on the principles of electrochemistry. An electrochemical reaction is
one in which electrons are transferred from one chemical species to another as the
chemical reaction is taking place. In a battery these reactions take place at the electrodes
of the battery. At the battery electrode known as the anode a reaction takes place known
as oxidation. During oxidation a chemical species loses electrons. The other electrode in
a battery is known as the cathode. Reaction known as reduction occurs at the cathode
where by electrons are combined with ions to form stable electrically balanced chemical
species. Batteries take advantage of these reactions by making the electrons formed by
oxidation on the anode flow through a wire to the cathode where they are used in the
reduction reaction. A load can be attached along this circuit in order to take advantage of
the current of electrons in order to power a device. Electrons move through the wire from
the anode to cathode because the conductive nature of the wire connecting the two makes
that path the easiest way for the electrons to get there.

The rechargeable, or secondary, batteries can be distinguished on the following
parameters. Voltage, current (maximum, steady state and peak), energy density (watt-
hours per kilogram and per liter), power density (watts per kilogram and per liter), and
service life (cycles to failure) and cost (per kilowatt hour).

The energy density per unit volume (Wh/1) and per unit weight (Wh/kg) of various
rechargeable batteries is shown in Fig. 1 (not all batteries fall within the ranges shown).
In the case of conventional batteries for instance, these systems contain a liquid
electrolyte, generally a concentrated aqueous solution of potassium hydroxide or
sulphuric acid. The use of aqueous battery electrolytes theoretically limits the choice of
electrode reactants to those with decomposition voltages less than that of water, 1 .23 V at
25 °C, although because of the high over potential normally associated with the
decomposition of water, the practical limit is some 2.0 V. The liquid state offers very
good contacts with the electrodes and high ionic conductivities but anion and cation
mobilities are of the same order of magnitude and their simultaneous flow gives rise to
two major problems: (i) corrosion of the electrodes, (ii) consumption of the solvent
(water) by electrolysis during recharging and by corrosion during storage, making
necessary periodic refilling. In addition, these two processes give off gases, thereby
prohibiting the design of totally sealed systems.

Energy Sources - A Chemist's Perspective

137

99
S

175

150

125

100

|j 200? year''
I at present

n
- | u

£ Lithium Ion

Lead Acid

-L.

50 100 150 200 250 300
Energy density per volume ( Wh l 1 )

Fig. 1 . Energy density of secondary batteries

350

The resulting problems include leakage of the corrosive electrolyte and air entries which,
even when kept to a minimum, deteriorate the electrolyte and the electrodes. A further
drawback is the risk of electrode passivation; the formation of insulating layers of PbS04,
Zn(OH) 2 on the electrodes.
2. Solid state electrolytes

The demand for batteries with high energy densities has inevitably led to research and
development of systems utilizing thermodynamically more stable to aqueous electrolytes.
The essential requirements of an electrolyte are that:
(1) It is ionically but not electronically conducting;

(2) It is neither a solvent for the reactants nor, preferably, for the reaction product and

(3) It has the decomposition potential grater than that of the chosen reaction product.

It is advantageous for the electrolyte to be inexpensive, non toxic and to have a low vapour
pressure. In general these requirements can be met in three classes of compounds; (1)
molten salts (2) ionically conducting solids and (3) organic liquids and low melting solids.
The concept of an all solid state battery is appealing since such a system would posses a
number of desirable characteristics: e. g. absence of any possible liquid leakage or gassing,

138

Solid State Batteries

the likelihood of extremely long shelf-life and the possibility of operation over a wide
temperature range. Solid state batteries could be constructed with excellent packaging
efficiency for the active components, without separators and using simple lightweight
containers. The opportunities for extreme miniaturization and very simple fabrication
techniques are of obvious importance in applications and reliability are key factors, as for
example in implantable electronic instrumentation such as cardiac pacemakers,
physiological monitoring /telemetry packages etc.

A solid electrolyte is a phase which has an electric conductance wholly due to ionic motion
with in the solid. Further, the only mobile charge carrier is the cation A + associated with an
anion immobilized in a crystal lattice. Such phases have been known for over a century, but
until recently all known materials of this type had high resistivities at ambient
temperatures. This high internal resistance of the cells is a direct result of the lack of any
ambient temperature solid with fast ion conduction. The most ionic conducting material at
that time was Agl with a conductivity value of about 10~ 6 S/cm at 25 °C. Table 1 shows the
five solid electrolyte batteries that were under development and as indicated the very high
internal resistance ranging from 50 kH up to 40 MH. This restricted the development of
solid electrolyte devices in a number of laboratory cells, used for thermodynamic studies,
and of little interest in power sources.

At room temperature solid electrolytes did not conduct current very well. A value of 10~ 6
S/cm was a high value of conductivity for a solid electrolyte. A striking development
occurred towards the end of 1960 with the discovery of a series of solids of general
formula MAg 4 I 5 (M=Rb, K ...) having exceptionally high ionic conductivity (> 10 Sm" 1 at
room temperature).
Table 1. Solid state batteries as of the year 1960

System

Cell potential

Development organization

Ag/Agl/V 2 5

0.46

National Carbon

Ag/AgBr/CuBr 2

0.74

General Electric

Ag/AgBr-Te/CuBr 2

0.80

Patterson-Moos Research

Ag/AgCl/KICl 4

1.04

Sprague Electric

Ni-Cr/SnS0 4 /Pb0 2

1.2-1.5

P.R. Mallory & Ray o vac

Energy Sources - A Chemist's Perspective

139

A number of structural features have been found to characterize solids with high ionic
conductivity and to distinguish them from the more usual ionic crystals. Ionic
conductivities of some solid state electrolytes are shown in Fig. 2.

a-LijSO,

a-Agl

cone. H 2 S0 4

Fig. 2. Ionic conductivity of some good solid electrolytes

The electrolyte is a solid fast ion conductor. The blocking of the anions prevents
passivation, corrosion and solvent electrolysis reactions. Consequently there is no gas
formation. It is therefore possible to design totally sealed batteries, eliminating the
deterioration of the electrolyte and the electrodes by the outside environment. Under
these conditions, the electrolyte can coexist with couples which are highly reducing at the
negative electrodes and highly oxidizing at the positive electrode. In such systems higher
energy densities can be achieved.

2.1. Ionic conductivity in solids electrolytes (Fast ion conductors)
Point defects are responsible for possible movements of atoms or ions through the
structure. If a crystal structure is perfect it would be difficult to envisage how the atoms
move, either by diffusion though the lattice or ionic conductivity (ion transport under the
influence of an external electric field). There are two possible mechanisms for the
movement of ions through a lattice: vacancy mechanism (it can be described as the

140 Solid State Batteries

movement of a vacancy rather than the movement of the ion) or interstitial mechanism
where an interstitial ion jumps or hops to an adjacent equivalent site. This simple picture
of movement in an ionic lattice are known as the hopping model (Fig. 3.).

OOOOOO OOOOC^DOO

oooooooo oooooooo

Fig. 3. Ion motion via point defects (a) mobile vacancy (b) mobile interstitial

Ionic conductivity a is defined in the same way as electronic conductivity
a = n q (j,

where n is the number of charge carriers per unit volume, q is their charge and \i is their
mobility, which is a measure of the drift velocity in a constant electric field. This
equation is a general equation defining conductivity in all conducting materials. In order
to understand why some ionic solids conduct better then others it is useful to look at the
definition more closely in terms of the hopping model. In the case of crystals where the
ionic conductivity is carried by vacancy or interstitial mechanism, the concentration of
charge carrier n will be closely related to the concentration of defects in the crystal, and \i
will thus refer to the mobility of these defects in such cases. Fast ion transport in
crystalline solids appears to be limited to compounds in which either Group IA or IB
cations or Group VI-A or VII-A anions are mobile, with cation conductors being far more
numerous. Typical examples of compounds in each of these categories include a-Agl,
Nap-Al 2 03, cubic stabilized Zr0 2 and P-PbF 2 respectively.
3. Solid state batteries

A solid-state battery is an energy converter transforming chemical energy into electrical
energy by means of internal electron exchange. The electron transfer is mediated by
mobile ions released from an ion source, the anode, and neutralized in the electron
exchanger, the cathode. The positive ion is transmitted through a dielectric, which is a

Energy Sources - A Chemist's Perspective

141

good electronic insulator, the separator. The ideal solid-state battery should be based on
one unique material in which three regions, corresponding to the ion source, the separator
and the electron exchanger, are separated only by internal homo junctions. The
conventional structure of the battery available today is shown in Fig. 4.

Anode

Fast-ion conductor

Cathode

Substrate

Fig. 4. Schematic representation of the construction of a solid-state micro battery.

The materials constituting the electrochemical cell are the ion source (anode), the
separator and the electron exchanger (cathode). The anode emits positive ions into the
separator and supplies the external circuit with electrons obtained from the oxidation
process. The ion-conducting separator is permeable only to the positive ions. The electron
exchanger allowing the reduction process accepts electrons from the external circuit and
positive ions through intercalation.

The discharge of the battery occurs when the battery is connected to an external load with
the metal ion source as negative and the intercalation compound as positive. An
electrochemical cell is then formed and the spontaneous oxidation-reduction reaction is a
source of electrical energy.

142

Solid State Batteries

Fig. 5. Schematic representation of the energy band diagram of a solid-state battery.

Table 2. Chronology of solid electrolyte batteries (1950-1990)

Date

Electrolyte

Log (S/cm)

Typical cell system

1950-60

Agl

-5

Ag/V 2 5

1960-65

Ag 3 SI

-2

Ag/I 2

1965-70

RbAg 4 I 5

-0.5

Li/Me 4 NI 5

1970-75

Lil

Li/I 2 (P2VP)

1970-75

LiI(Al 2 3 )

Li/Pbl 2

1970-75

p-alumina

1.5

Na-Hg/I 2 ,PC

1980-85

LiI a O b S c P d

-3

Li/TiS 2

1978-85

LiX-PEO

-7

Li/V 2 5

1983-87

MEEP

-4

Li/TiS 2

1985-90

Plasticized SPE

-3

Li/V 6 3

When the cell is connected to an external load, electrons are extracted from the metal and
flow into the external circuit. Positive ions are injected into the separator and diffuse
toward the insertion material cathode. Once transferred into the cathode the positive ions
are distributed near the surface to from a space charge layer. The quasi-Fermi level now
depends on the distribution of charges in each material. A very thin layer of negative

Energy Sources - A Chemist's Perspective 143

charge is formed at the metal-insulator surface to compensate for the positive charges
distributed throughout the insulator. A space charge layer is formed in the semiconductor
interface to account for the ion injection into the intercalation compound. The energy
band diagram for a solid-state battery is represented in Fig. 5.

It is convenient to classify solid state batteries into four classes: high temperature,
polymeric, lithium and silver. A summary of the chronology of solid state electrolytes
and ambient temperature solid state batteries that were investigated during 1950 to 1990
is given in Table 2.

3.1. High temperature cells

The alkali metals lithium and sodium are attractive as battery anodes on account of their
high electrode potentials and low atomic masses, which together result in excellent values
for the battery specific energy. Batteries that consists of solids (fast ion conductors) or
fused salts as electrolytes and which operate at temperatures of 200-500 °C are
considered.

3.2. Silver ion batteries

Agl exhibits an unusually high ionic conductivity at elevated temperatures which
decreases -20% upon melting. Silver iodide is known to go through a phase transition at
146 °C to the high conducting phase, which is accompanied by an increase in
conductivity of three orders of magnitude. Attempts to stabilize the high temperature a-
Agl phase to room temperature by substituting foreign ions or complexes for either silver
or iodine have been rather successful. These modified Agl conductors are classified in the
following categories,

(a) Anion substituted; e.g., S 2 ", P0 3 " 4 , P 2 7 4 ", S0 4 ", W0 4 ",

(b) Cation substituted; e.g., K + , Rb + , or NH + ions to produce the MAg 4 I 5 class of
compounds,

Other Ag conducting FICs based on the silver chalcogenides (Ag2X, X = S, Se, Te) have
been developed in a like manner.

The first commercial solid-state battery was manufactured at the end of the 1960's in the
USA by Gould Ionics: this was a silver-iodine battery using RbAg 4 I 5 . Silver halides and
rubidium silver iodide provide a very high Ag + ion conductivity. RbAg 4 I 5 exhibits a

144

Solid State Batteries

-i___-i

conductivity of 27 Q~ cm" at 25 °C, which is the highest value for all solid electrolytes at
room temperature. A schematic diagram of the cell providing power to an external circuit
is shown in Fig. 6.

Anode

"*Ag

Electrolyte

Ag +

Cathode

+ — ►

Load

Fig. 6. Schematic diagram of silver ion, solid-state battery

3.3. Solid-state primary lithium batteries

A major shortcoming of silver-based solid electrolytes, which limits galvanic cell
voltages, is their low decomposition potentials. An electrolyte with room temperature
conductivity approaching that of the silver compounds and possessing a high
decomposition potential would open up a wide range of applications. Many compounds
have been studied with that goal in mind. One such material is lithium iodide.
With its low density (0.53 g cm" 3 ), low electro negativity, and high electron/atom mass
ratio, lithium has become the preferred choice for the active element of the anode, which
on discharge functions as an electron donor according to

anode: x Li ► x Li + x e 1 discharge,

where Li enters the electrolyte and the electron exits the anode to the external circuit to
power the load. The elemental lithium is typically present in a host insertion material;
most commonly a lithiated carbon such as Li x C6. Fig. 7 shows a schematic representation
of a lithium battery in discharge mode.

Energy Sources - A Chemist's Perspective

145

The lithium-iodine battery has been used to power millions of cardiac pacemakers since
its introduction in 1972. The lithium-iodine has established a record of reliability and
performance unsurpassed by any other electrochemical power source. This battery has a
solid anode of lithium and a polyphase cathode of poly-2-vinylpyridine which is largely
iodine (at 90% by weight). The solid electrolyte is a thin Lil film. The cell has an open-
circuit voltage of 2.8 V and the energy density is 100 - 200 Wh kg" 1 . These batteries have
extended life time of 10 years for 150 to 250 mA h capacities.

Current

collector

(Cu)

■+> e

Anode

Load

■> e

LiMOv Carbon black Polymer binder

Electrolyte

Cathode

Fig. 7. Schematic representation of a rechargeable lithium battery in discharge mode.

The main problem areas in primary solid state batteries have been identified as: (i)
volume changes, (ii) electrolyte impedance, (iii) discharge product impedance, (iv)
materials compatibility and (v) manufacturability. Solid-state primary batteries can
provide generally very long-life at low currents. Another example of such batteries is the
lithium-glass batteries whose envisaged applications are mainly as power sources in
electronic computers for CMOS memory back up.
3.4. Sodium batteries

Sodium is most attractive as a negative electrode reactant on account of its high
electrochemical reduction potential of 2.271 V. When coupled with an appropriate
electropositive material, it is capable of giving a cell of voltage >2 V. Moreover, sodium

146 Solid State Batteries

is abundant in nature, cheap and non-toxic. It is also of low atomic mass (23.0) and the

combination of high voltage and low mass leads to the possibility of a battery of high

specific energy. The realization of a practical battery based on sodium depended upon

identifying a suitable non aqueous electrolyte. The sodium sulphur battery is the best

developed solid electrolyte battery. It comprises a molten sodium negative electrode and

a molten sulphur positive electrode separated by a sodium ion conducting solid. Sodium

P- and P "-alumina are non stoichiometric aluminates, that typically are synthesized from

NaO and alumina.

Sodium beta alumina is highly conductive towards Na + ions at 300 °C, while being a

good electronic insulator. This gave rise to the possibility of a solid ceramic electrolyte.

The cell discharges in two steps as Na + ions pass through the beta alumina to the sulphur

electrode:

Step 1 2Na + 5S ^=> Na 2 S 5 E° = 2.076 V

Step 2 2xNa + (5-x)Na 2 S 5 i=> 5 Na 2 S 5 . x ( o<x<2) E° = 2.076 — *1 .78 V

In the first step, sodium polysulphide (Na 2 S5) is formed as a liquid, immiscible with

liquid sulphur. The open circuit voltage is therefore invariant at 2.076 V. Once all the

sulphur has been converted to Na 2 Ss, an ionic conducting liquid, further discharge to

Na 2 S3 takes place in a single phase and therefore the voltage declines linearly to 1 .78 V at

the composition Na 2 S3. These reactions are fully reversible on recharge. The sodium

aluminum oxide phase diagram is complex and a great deal of work has gone into

optimizing sodium beta alumina ceramic for this application.

The sodium sulphur cell, shown schematically in Fig. 8, can store several times more

energy per weight and volume than a conventional lead acid battery. Typical

characteristics at 300 °C are with an open circuit Voltage of 2.18 V, an energy density of

200 W h kg" 1 and a capacity of 15 Ah. When cells are assembled into a battery, this

figure will be degraded and a value of 150 W h kg" 1 for a complete battery should be

attainable. Despite their very intensive development, sodium sulphur batteries are

essentially dead because of the inability to maintain a consistent quality. It is possible to

replace p-alumina by a Na— conducting borate glass and other materials such as Nasicon

of composition Nai_ x ,Si x Zr 2 P3- x Oi 2 (with 1.8<x<2.4) have been crystal engineered to

maximize conductivity and ease of fabrication .

Energy Sources - A Chemist's Perspective

147

Charge lever

Activ*

Discharge level

Gasket seals

Case, also acting as
current collector

Felt impregnated
with sulphur,
with expansion
volume

-TL

Alumina collar
Gas seal

- Nut

Redundant sodium

Beta-alumina
Solid electrolyte

Fig. 8. Schematic of sodium/ sulphur cell

3.5. Solid state secondary lithium batteries
3.5.1. Lithtum iron sulphide batteries

One of the very few examples of a commercial solid state battery is the lithium heart
pacemaker power source, but many systems of potential applicability have been proposed
during the last 15 years. The Solid-state rechargeable batteries are with very low
capacity, generally of the order of mille Ampere hours, and yet research and development
effort are engaged, the target is the CMOS memory back up. Variety of solid electrolytes
and intercalation cathode materials are used. The general structure of the cell is solid
lithium anode, fast- ion conducting glass electrolyte and layered intercalation compound
cathode. An example is the cell Li/LiBF 4 -PC/CFx with a cell voltage of 2.8 V and
energy density 320 Wh kg" 1

148 Solid State Batteries

The lithium iron sulphide battery operates at 400-500 °C using a fused halide eutectic
electrolyte immobilized in the pores of a suitable separator. The most commonly used
electrolytes are the LiCI-KCl binary eutectic and the LiF-LiCI-LiI ternary lithium
halides. With Li-Al alloy anodes, two distinct voltage plateaus are observed at 1.6 and
1.35 V. Most development work has concentrated on the LiAl/FeS couple and the Varta
Battery Company has produced a series of 140 A h cells with a specific energy of 100 W
h kg" 1 at low discharge rates of 80 mA cm' 2 , falling to 50 W h kg" 1 at high rates of 250
mAcm" 2 There are still a number of unresolved .scientific questions on the chemistry of
LiAl/ FeS cells and the mechanism of the degradation and failure. In this system the
separator is clearly a crucial component which must not only keep the electrode materials
apart but also allow good permeation of the electrolyte and the most suitable materials are
found to be boron nitride and zirconia in the form of woven cloths but there are obviously
very expensive options.
3.5.2 Polymeric batteries

Polymer electrolyte batteries have been under development for cells operable at elevated
temperatures (60-140°C). An experimental battery uses a thin electrolyte film made from
a polymer such as polyethylene oxide (PEO) to separate the lithium electrode from an
ion-insertion-type electrode such as VeOn, TiS2 or V3O8.

In many developmental cells, the positive electrode (cathode) is a composite and consists
of small particles of insertion compound bound together with polymer electrolyte and
carbon which improves its electronic conductivity (Fig. 9). The composite electrode (50-
75|j,m thick) is deposited on a thin copper or nickel current collector less than 25 |jm and
a film (25-50|j,m) of [(C2H 4 0)9 LiF 3 CS03] n , polymer electrolyte completes the lithium
cell. Another possibility is to roll the cell assembly. A cell of this type using VeOn as the
composite positive electrode would have a potential of about 2.8 V. During discharge, at
currents of around 1 mA cm" 2 the voltage stabilizes around 2 V. The practical energy
density is in the order of 200W h kg" 1 , the power density reaching 0.1 W g" 1 . The main
application envisaged is storage batteries for all electric vehicles.
The immediate advantages, expected from polymer technology in electrochemistry, are
good mechanical properties, easy processing and lightweight materials.

Energy Sources - A Chemist's Perspective

149

The polymer salt phases transform to resistive phases at lower temperatures and
consequently little development has been reported at normal ambient temperatures. Cells
have been reported, operated at 26 °C with M0O2 cathodes from which it is projected that
energy densities in the range 0.1-0.2 W h cm" 3 may be achieved

composite electrode

polymeric

electrolyte carbon

v 6 o 13

Fig. 9. Schematic representation of a polymeric lithium cell using a composite electrode.

3.5.3. Lithium halogen batteries

The theoretical specific energy for the Li/Lil/I 2 (P2VP) cell is 1 .9 W h cm" 3 commercially
available lithium/iodide batteries have a solid anode of lithium and a polyphase cathode
(poly-2-vinyl pyridine) which is largely iodide (at 90% by weight). The discharge
reaction is

2 Li + P2VP nl 2 ► P2VP(n - 1 I 2 + 2 Lil

This cell has an open circuit voltage of 2.8 V. The electrolyte ionic conductivity is 6.5 x
10" 7 S cm" 1 at 25 °C, and the energy density is 100-200 W h kg" 1 .

Batteries of medium capacities (up to around 1 A h) can be used for random access
memory power supplies in electronics. Similar batteries using Li/Br have also been built.
The greater electronegative bromine gives rise to voltages of the order of 3.5 V and

150 Solid State Batteries

energy densities are as high as 1.25 W h cm" 3 Their practical application is however
limited by the limited conductivity of the LiBr films formed.

3.6. Thin film batteries using copper ion conductors

Although copper ion conducting materials are well known, applications in thin film micro
batteries are very rare. One example is a battery with bimetal electrodes sandwiching a
Cu- conductor. The latter was prepared by an electrolytic deposition method giving a
Cul- CuCl mixture on a copper anode surface. Many other metals could be used on the
other side. In all cases a low voltage was obtained, between 0.26 V (chromium) and 1.3 V
(magnesium).

3.7. Lead-cupric fluoride thin layer batteries

This is a system which is interesting mainly because of its concentration and its method
of fabrication. The cell is based on the fluoride ion solid conductor, (3-PbF 2 . The ionic
conductance of this material is low at room temperature (~5 x 1 — 5 Sm" 1 ). In this cell
lead metal used is the negative electrode, PbF 2 is the electrolyte and CuF 2 is the positive
electrode. Because of the high resistivity of CuF 2 , it was co-deposited with PbF 2 , to form
a more conductive mixed layer. The reactions lead to a voltage of 0.7 V. A current
density of up to 10 mA cm" 2 could be obtained. This cell was not rechargeable. Other
works are reported on micro batteries using PbFe (or derived structures) or other F
conductors as the electrolyte.

Anode: Pb + 2F" ► PbF 2 + 2e"

Cathode: CuF 2 + 2e" ► Cu + 2F"

Lead was always the negative electrode and BiF 3 often the positive electrode. In these
cases the system was rechargeable. Current densities of 40 |jA cm" 2 at 0.2 V were
obtained. More recently the use of an evaporated mixture of PbF 2 , and LiF as the
electrolyte was mentioned.

So far, the diverse research activities that led to the development of cathode and anode
active materials, separator, electrolyte, current collector (metal foil; cathode is aluminum
foil and anode Cu foil), material optimization and possible materials for use in a lithium
ion battery have been described.
4. Manufacturing process

Energy Sources - A Chemist's Perspective

151

The manufacturing processes consist of (1) mixing the cathode or anode materials with
binder and conductive additive, (2) painting on the current collector (metal foil), (3)
drying and (4) pressing. The next step involves (1) assembly of cathode, anode and the
simultaneous rolling-up with separator, (2) electrode insertion, (3) electrolyte injection
into the battery case and (4) sealing.

In the electrode manufacturing process, a mixture of active materials with conductive
additive such as acetylene black or Ketjen black, and a binder such as Teflon or
polyvinylidenefluoride (PVF) dissolved in n-methyl-2-pyrrolidinone (NMP) are made in
the form of a paste. The paste is painted over both sides of metal foil, dried and roll-
pressed. Then it is cut to the desired width. In the case of polymer lithium batteries, after
carrying out direct polymerization of the gel electrolyte sheet, roll-press is carried out
over the cathode and anode sheets which are then cut a suitable size, wrapped in
aluminum lamination film and heat welded at the edges (Fig. 10).

grid

cathode
materials

polymer film
(separator)

anode ,
materials

Cugrid

Fig. 10. Schematic manufacture processing of lithium polymer battery

Finally, the battery is checked for short-circuit over 2-4 weeks. A protective thin film
(SEI) will form at the anode-carbon interface during this period. Shipment inspection has
to be conducted and the products shipped. Many battery manufacturing companies

152 Solid State Batteries

worldwide have announced their involvement in large-scale production of lithium
secondary batteries. However, the level of information released is limited and thus, it is
impossible to evaluate the status of the different batteries at this stage.

References

1 . A. Levasseur. M. Menetrier, R. Dormoy and G. Meunier, Material Science and
Engineering B, 3 (1989) 512.

2. B. B. Owens P. M. Skarstad, Solid State Ionics, 53-56 (1992) 665-672

3. R.M. Dell, Solid State Ionics, 134 (2000) 139-158.

4. Vincent C.A., Modern Batteries (2nd Edition), Edward Arnold, London (1998).

5. Gabano J.-P. (Ed.), Lithium Batteries, Academic Press (1983)

Chapter - 9

FUEL CELLS

Ch. Venkateswara Rao

1. Introduction

During the past decade, fuel cells received enormous attention all over the world as novel
electrical energy conversion systems. The major factor that influences the development of
fuel cells over the last few years is the world wide concern on the environmental
consequences of the use of fossil fuels in the production of electricity and for the
propulsion of vehicles. The dependence of the industrialized nations on oil crisis and,
recently, pressure on fossil fuels reserves is a cause of anxiety. More importantly
however, is the increasing social awareness, over the last few decades, concerning issues
of environmental pollution. The combustion of fossil fuels releases harmful emissions
into air which influence the greenhouse effect as well as direct health problems of human
beings. Major emissions of NO x , SO x , CO2 and particulate matter are the cause of
majority of the concern for pollution of the environment resulting in the increase of ozone
level in the lower atmosphere, acid rain and warming of the atmosphere. Particulate
matter or soot produced from combustion in vehicle engines, power plants and industrial
processes can penetrate into the lungs and cause variety of health problems. There are
several ways in which the emission by the human activities can be curbed and the
dependence on the fossil fuels reduced without diminishing the standard of living.
Besides, the enormous potential of saving energy, the efficiency of the end-use
equipment, of vehicle propulsion engines as well as power generation facilities can be
improved. The contribution of renewable energy sources from wind, sun and water could
increase but the complete generation process should be taken into account when
comparing different systems and these sources are not suited to cover the base load.
Therefore, it appears that the solar energy or other renewable sources cannot meet the
energy demand substantially. The future of the world is critically energy dependent.
Many consider the effect of new technologies leading to the better utilization of the fuels,
in addition to the use of solar and other renewable energies including the proper use of

154 Fuel Cells

atomic energy. The higher efficiencies and lower emissions make the fuel cells a valuable
contribution to the power generation facilities, even though its contribution to the total
energy demand may be minimal. All these issues indicate that the fuel cells appear to be
one of the alternate energy sources that can cater to the needs of future world. The 19 l
century was considered to be the age of the Steam Engine while the 20 l century is
considered as the age of the Internal Combustion Engine and 21 st century may come to be
recognized as the age of the Fuel Cells.

The invention of fuel cells as an electrical energy conversion system is attributed to Sir
William Grove; however, the principle was discovered by Christian Friedrich Schonbein.
Sir William Grove mixed hydrogen and oxygen in the presence of an electrolyte, and
produced electricity and water and called it as a gaseous voltaic battery. The invention,
which later came to be known as a fuel cell did not produce enough electricity to be
useful. In 1889, the term 'fuel cell' was first given by Ludwig Mond and Charles Langer,
who attempted to build a working fuel cell using air and industrial coal gas. Although
William Grove first demonstrated in 1839, it was used only in 1960 for space
applications.
2. What is a fuel cell?

A fuel cell is an electrochemical energy converter that converts chemical energy of fuel
into DC electricity, heat and water. Typically, a process of electricity generation from
fuels involves several energy conversion steps, namely:

1 . combustion of fuel converts chemical energy of fuel into heat,

2. this heat is then used to boil water and generate steam,

3. steam is used to run a turbine in a process that converts thermal energy into mechanical
energy, and finally

4. mechanical energy is used to run a generator that generates electricity.

Thermal energy

► Mechanical energy

Chemical energy
of fuels

Fuel Cells

Scheme 1. Direct energy conversion with fuel cells in comparison to conventional
indirect technology

An Introduction to Energy Sources 155

A fuel cell circumvents all these processes and generates electricity in a single step
without involving any moving parts. Such a device must be simpler, thus less expensive
and far more efficient than the four-step process previously depicted.
Unlike conventional internal combustion engine, higher efficiencies are achievable in
fuel cells as they do not suffer from Carnot's limitations. A fuel cell is in some aspects
similar to a battery. It has an electrolyte, and negative and positive electrodes, and it
generates DC electricity through electrochemical reactions. However, unlike a battery, a
fuel cell requires a constant supply of fuel and oxidant. Also, unlike a battery, the
electrodes in a fuel cell do not undergo chemical changes. Batteries generate electricity
by the electrochemical reactions that involve the materials that are already in batteries.
Because of this, a battery may be discharged, which happens when the materials that
participate in the electrochemical reactions are depleted. Some batteries are rechargeable,
which means that the electrochemical reactions may proceed in reverse when external
electricity is applied - a process of recharging the battery. A fuel cell cannot be recharged
as long as the reactants-fuel and oxidant-are supplied.

Fuel cells have many applications that make them attractive when compared with the
existing conventional energy conversion technologies, namely:
(i) Promise of high efficiency
(ii) Promise of low or zero emissions
(iii) Simplicity

(iv) No moving parts and promise of long life
(v) Quiet

Fuel and size flexibility

Because of their attractive properties, fuel cells have already been developed and come
into widespread commercial use through three main applications: transportation,
stationary power generation and portable applications.
3. Choice of fuel and oxidant

The choice and design of the fuel cell depend on the kind of fuel and oxidant adopted,
operating temperature, power rating/conditioning and other usage requirements. A fuel-
cell system that includes a fuel reformer can utilize the hydrogen from any hydrocarbon
fuel, from natural gas to methanol, and even gasoline. Gaseous hydrogen has become the

156 Fuel Cells

fuel of choice for most applications, because of its high reactivity when suitable catalysts
are used, its ability to be produced from hydrocarbons for terrestrial applications, and its
high energy density (32 kWh/kg) when stored cryogenically for closed-environment
applications, such as in space. Similarly, the most common oxidant is gaseous oxygen,
which is readily and economically available from air for terrestrial applications and is
also easily stored in a closed environment. In general, the oxygen needed by a fuel cell is
generally supplied in the form of air.
4. How does a fuel cell works?

The basic physical structure or building block of most fuel cells consists of an electrolyte
layer in contact with porous anode and cathode electrodes on either side. All fuel cells
have similar basic operating principle. The input fuel is catalytically reacted (electrons
removed from the fuel) in the fuel cell to create an electric current. The input fuel passes
over the anode is catalytically split into electrons and ions. Air/oxygen passes over the

Air — ►■ Cb-

Fuel

Fig.l. Schematic of a fuel cell
cathode is reduced by the electrons which are generated at anode and passed on to the
cathode by external circuit. At cathode, the ions which are formed at anode and
transported to cathode through the electrolyte, combine with the oxide ions and generate
the oxidized product. If the fuel happens to be hydrogen, then water is formed.

4.1. Thermodynamical and kinetic aspects of electrochemical energy transformation
The energy storage and power characteristics of electrochemical energy conversion
systems follow directly from the thermodynamic and kinetic formulations for chemical
reactions as adapted to electrochemical reactions.

4.2. Thermodynamics

The basic thermodynamic equations for a reversible electrochemical transformation are
given as

AG = AH - TAS

An Introduction to Energy Sources 157

where AG is the Gibbs free energy, or the energy of a reaction available for useful work,

AH is the enthalpy, or the energy released by the reaction, AS is the entropy, and T is the

absolute temperature, with TAS being the heat associated with the

organization/disorganization of materials. The terms AG, AH, and AS are state functions

and depend only on the identity of the materials and the initial and final states of the

reaction.

Effect of temperature on free energy change (Gibbs-Helmholtz equation) is given by

AG = AH + T(d(AG)/ 5T) p

(<9(AG/T)/<9T) p = -AH/T 2

Effect of pressure on free energy change is given by

(<9(AG)/3P) T = AnRT/P

The maximum electrical work (W e i) obtainable in a fuel cell operating at constant

temperature and pressure is given by the change in Gibbs free energy (AG) of the

electrochemical reaction:

AG = -nFE — (1)

and

AG = -nFE° — (2)

where n is the number of electrons transferred per mole of reactants, F is the Faraday

constant, being equal to the charge of 1 equiv of electrons, and E is the voltage of the cell

with the specific chemical reaction; in other words, E is the electromotive force (emf) of

the cell reaction. The voltage of the cell is unique for each reaction couple. The amount

of electricity produced, nF, is determined by the total amount of materials available for

reaction and can be thought of as a capacity factor; the cell voltage can be considered to

be an intensity factor. The usual thermodynamic calculations on the effect of temperature,

pressure, etc., apply directly to electrochemical reactions. Spontaneous processes have a

negative free energy and a positive emf with the reaction written in a reversible fashion,

which goes in the forward direction. The van't Hoff isotherm identifies the free energy

relationship for bulk chemical reactions as

AG = AG + RT ln(Q); Q = A P /A R

158

Fuel Cells

where R is the gas constant, T the absolute temperature and Q is the term dependent on
the activity of reactants (A R ) and products (A P ).

Combining eq (1) and (2) with the van't Hoff isotherm, one obtain the Nernst equation
for electrochemical reactions:

E = E° - RT/nF ln(Q)
According to the Nernst equation for hydrogen-oxygen reaction, the ideal cell potential
depends on the cell temperature, pressure of reactants, etc. The impact of temperature on
the ideal voltage, E, for the oxidation of hydrogen is shown in Fig. 2.

> 1-2-

'£
?

1.1 —

1.0

300 400 500 600 700 800 900 1000 1100

Temperature (K)

Fig.2. H2/O2 fuel cell ideal potential as a function of temperature

At a given temperature, the ideal cell potential can be increased by operating at higher

reactant pressures, according to the equation

E = E° + (RT/2F) In [P H 2 /P H 2 0] + (RT/2F) In [P 1/2 2 ]

and improvements in fuel cell performance have, in fact, been observed at higher

pressures.

4.3. Kinetics

Thermodynamics describe reactions at equilibrium and the maximum energy release for a

given reaction. Useful work (electrical energy) is obtained from a fuel cell only when a

reasonable current is drawn, but the actual cell potential is decreased from its equilibrium

potential because of irreversible losses. Figure 3 shows a typical voltage-current (E - I)

discharge curve for a fuel cell with an open-circuit voltage E oc . The overpotential r\ = (E oc

- E) reflects the resistive IR losses due to the surface reaction kinetics, the resistance to

transport of the working ion, H + or O 2 " between the reductant and the oxidant reactive

An Introduction to Energy Sources

159

sites, and the resistance to diffusion of the oxidant and/or reductant to the catalytic sites
and their products away from these sites. At low currents, the performance of a fuel cell
is dominated by kinetic losses. These losses mainly stem from the high overpotential of
the reactions occurred at anode and cathode. At intermediate currents, ohmic losses arise
from ionic losses in the electrodes and separator, although contact and electronic
resistances can be important under certain operating conditions. At high currents, mass
transport limitations become increasingly important. These losses are due to reactants not
being able to reach the electrocatalytic sites. Typically, oxygen is the problem due to
flooding of the cathode by liquid water, but protons and electrons can also cause mass-
transfer limitations.

CellE

Current

Fig. 3. Typical polarization curve for a fuel cell: voltage drops due to: (i) surface
reaction kinetics; (ii) electrolyte resistance; and (iii) reactant/product diffusion
rates

At low current densities (i < 1 mA cm" 2 ), electrodes gives a larger R tr and therefore
overpotential, r\ should be greater than 400 mV (at room temperature). An extremely
active electrocatalyst is needed to overcome this initial voltage drop in the E versus
current discharge curve. The goal of fuel cell developers is to minimize the polarization
so that Eceii approaches Eoc. This goal is approached by modifications to fuel cell design
(improvement in electrode structures, better electrocatalysts, more conductive electrolyte,
thinner cell components, etc.). For a given cell design, it is possible to improve the cell

160 Fuel Cells

performance by modifying the operating conditions (e.g., higher gas pressure, higher
temperature, change in gas composition to lower the gas impurity concentration).
However, for any fuel cell, compromises exist between achieving higher performance by
operating at higher temperature or pressure and the problems associated with the
stability/durability of cell components encountered at the more severe conditions.
4.4. Fuel cell efficiency

The ideal or maximum efficiency of an electrochemical energy converter depends upon
electrochemical thermodynamics whereas the real efficiency depends on electrode
kinetics. The thermal efficiency of an energy conversion device is defined as the amount
of useful energy produced relative to the change in stored chemical energy (commonly
referred to as thermal energy) that is released when a fuel is reacted with an oxidant.

s = Useful energy/ AH
In the ideal case of an electrochemical converter, such as a fuel cell, the change in Gibbs
free energy, AG, of the reaction is available as useful electric energy at the temperature of
the conversion. The ideal efficiency of a fuel cell, operating irreversibly, is then

s = AG/AH
The most widely used efficiency of a fuel cell is based on the change in the standard free
energy for the cell reaction, for example,

H 2 +'/ 2 2 ^H 2 0(l)
given by

AG ° = G H 2 G H 2 -' /2G 2

where the product water is in liquid form. At standard conditions of 25 °C (298 K) and 1
atmosphere, the chemical energy (AH) in the hydrogen/oxygen reaction is 285.8 kJ/mole,
and the free energy available for useful work is 237.1 kJ/mole. Thus, the thermal
efficiency of an ideal fuel cell operating reversibly on pure hydrogen and oxygen at
standard conditions would be:

£ideai = 237.1/285.8 = 0.83
The efficiency of an actual fuel cell can be expressed in terms of the ratio of the operating
cell voltage to the ideal cell voltage. The actual cell voltage is less than the ideal cell

An Introduction to Energy Sources 161

voltage because of the losses associated with cell polarization and the iR loss. The
thermal efficiency of the fuel cell can then be written in terms of the actual cell voltage,
s = Useful energy/ AH = Useful power/(AG/0.83)
= (Volts ac tuai x Current)/(VoltSideai x Current/0.83)

= 0.83 (V0ltS actua l)/(V0ltS ld eal)

As mentioned, the ideal voltage of a cell operating reversibly on pure hydrogen and
oxygen at 1 atm pressure and 25 °C is 1.229 V. Thus, the thermal efficiency of an actual
fuel cell operating at a voltage of E ce ii, based on the higher heating value of hydrogen, is
given by

Sideal = 0.83 X Ecell/Eideal = 0.83 X E ce ll/1 .229 = 0.675 X E ee ll

A fuel cell can be operated at different current densities, expressed as mA/cm 2 or A/ft 2 .
The corresponding cell voltage then determines the fuel cell efficiency. Decreasing the
current density increases the cell voltage, thereby increasing the fuel cell efficiency. The
trade-off is that as the current density is decreased, the active cell area must be increased
to obtain the requisite amount of power. Thus, designing the fuel cell for higher
efficiency increases the capital cost, but decreases the operating cost.
5. What are the various types of fuel cells?

A variety of fuel cells are in different stages of development. They can be classified by
use of diverse categories, depending on the combination of type of fuel and oxidant,
whether the fuel is processed outside (external reforming) or inside (internal reforming)
the fuel cell, the type of electrolyte, the temperature of operation, whether the reactants
are fed to the cell by internal or external manifolds. The most common classification of
fuel cells is by the type of electrolyte used in the cells and includes 1) alkaline fuel cell
(AFC), 2) phosphoric acid fuel cell (PAFC), 3) proton exchange membrane fuel cell
(PEMFC), 4) direct methanol fuel cell (DMFC) 5) molten carbonate fuel cell (MCFC),
and 6) solid oxide fuel cell (SOFC). These fuel cells are listed in the order of approximate
operating temperature, ranging from -353 K for PEMFC, 333-353 K for DMFC, -373 K
for AFC, -273 K for PAFC, -923 K for MCFC, and 1273 K for SOFC. The operating
temperature and useful life of a fuel cell dictate the physicochemical and
thermomechanical properties of materials used in the cell components (i.e., electrodes,
electrolyte, interconnect, current collector.).

162

Fuel Cells

Aqueous electrolytes are limited to temperatures of about 200 °C or lower because of
their high water vapor pressure. The operating temperature also plays an important role in
dictating the type of fuel that can be used in a fuel cell. The low-temperature fuel cells
with aqueous electrolytes are, in most practical applications, restricted to hydrogen as a
fuel. In high-temperature fuel cells, CO and even CH 4 can be used because of the
inherently rapid electrode kinetics and the lesser need for high catalytic activity at high
temperature.

Fuel

AFC

H 2
H 2

PEMFC

DMFC

CH3OH

co 2

PAFC

MCFC

H 2

SOFC

H 2
H 2

-OH
H + ■
H + .
H + .

-CO, 2

O 2

o 2

H 2

o 2

H 2

o 2

H 2

o 2
co 2

Anode

Cathode

373 K

353 K

473 K

923 K

1273 K

Electrolyte

Fig. 4. Various types of fuel cells

Oxygen/air

The characteristic features of various types of fuel cells are shown in Table 1.
The heart of the fuel cell is membrane electrode assembly (ME A). The important
components and their tasks are given in Table 2. A significant problem is the control of
the interface at the junction of the reactant phase, the electrolyte medium, and the
catalyzed conducting electrode, the so-called "three-phase boundary", where the
electrolyte, electrode, and reactant all come together. A stable three-phase boundary is

An Introduction to Energy Sources

163

critical to good performance and long operation. Therefore, the porosity and the wetting
behavior with electrolyte and the electrode surface must be precisely adjusted.
Table 1. Characteristic features of various fuel cells

Electrochemical

Operating

Electrolyte

Charge

Electrolyte

Fuel for cell

Oxidant for cell

device

temp (K)

carrier

state

Alkaline fuel cell

333-423

45% KOH

OH"

Immobilized

Hydrogen

2 /Air

(AFC)

liquid

Phosphoric acid

453-493

H3PO4

Hydrogen

2 /Air

fuel cell (PAFC)

Proton exchange

333-353

Ion

Solid

Hydrogen

2 /Air

membrane fuel cell

exchange

(PEMFC)

membrane

(e.g.,
Nafion)

Direct methanol

333-353

))

H +

Solid

Methanol

2 /Air

fuel cell (DMFC)

Molten carbonate

923-973

Alkali

C0 3 2_

Immobilized

Hydrogen

2 /Air

fuel cell (MCFC)

carbonate
mixture

liquid

Solid oxide fuel

1073-1273

Yttria-

o 2 -

Solid

Hydrogen

2 /Air

cell (SOFC)

stabilized
zirconia

The electrodes have to be gas (or liquid) permeable and therefore possess a porous
structure. The structure and content of the gas diffusion electrodes is quite complex and
requires considerable optimization for the practical application. The functions of porous
electrodes in fuel cells are: 1) to provide a surface site where gas/liquid ionization or de-
ionization reactions can take place, 2) to conduct ions away from or into the three phase
interface once they are formed (so an electrode must be made of materials that have good
electrical conductance), and 3) to provide a physical barrier that separates the bulk gas
phase and the electrolyte. A corollary of first one is that, in order to increase the rates of
reactions, the electrode material should be catalytic as well as conductive, porous rather
than solid. The catalytic function of electrodes is more important in lower temperature
fuel cells and less so in high temperature fuel cells because ionization reaction rates
increase with temperature. It is also a corollary that the porous electrodes must be
permeable to both electrolyte and gases, but not such that the media can be easily
"flooded" by the electrolyte or "dried" by the gases in a one-sided manner.

164

Fuel Cells

Porous electrodes are key to good electrode performance.

Table 2. MEA (Membrane electrode assembly) components and their tasks

MEA component

Task/effect

Anode substrate

Anode catalyst layer

Proton exchange
membrane

Cathode catalyst layer
Cathode substrate

Fuel supply and distribution (hydrogen/fuel gas)

Electron conduction

Heat removal from reaction zone

Water supply (vapour) into electrocatalyst

Catalysis of anode reaction
Ion conduction into membrane
Electron conduction into substrate
Water transport
Heat transport

Ion conduction
Water transport
Electronic insulation

Catalysis of cathode reaction

Oxygen transport to reaction sites

Ion conduction from membrane to reaction sites

Electron conduction from membrane to reaction sites

Water removal from reactive zone into substrate

Heat generation/removal

Oxidant supply and distribution (air/oxygen)
Electron conduction towards reaction zone
Heat removal
Water transport (liquid/vapour)

The reason for this is that the current densities obtained from smooth electrodes are
usually in the range of a single digit mA/cm 2 or less because of rate-limiting issues such
as the available area of the reaction sites. Porous electrodes, used in fuel cells, achieve
much higher current densities. These high current densities are possible because the
electrode has a high surface area, relative to the geometric plate area that significantly
increases the number of reaction sites, and the optimized electrode structure has favorable
mass transport properties. In an idealized porous gas fuel cell electrode, high current
densities at reasonable polarization are obtained when the electrolyte layer on the
electrode surface is sufficiently thin so that it does not significantly impede the transport
of reactants to the electroactive sites, and a stable three-phase (gas/electrolyte/electrode

An Introduction to Energy Sources 165

surface) interface is established. When an excessive amount of electrolyte is present in
the porous electrode structure, the electrode is considered to be "flooded" and the
concentration polarization increases to a large value.

The porous electrodes used in low-temperature fuel cells (AFC, PAFC, PEMFC and
DMFC) consist of a composite structure that contains platinum (Pt) electrocatalyst on a
high surface area carbon black and a PTFE (polytetrafluoroethylene) binder. Such
electrodes for acid and alkaline fuel cells are described by Kordesch et al [2]. In these
porous electrodes, PTFE is hydrophobic (acts as a wet proofing agent) and serves as the
gas permeable phase, and carbon black is an electron conductor that provides a high
surface area to support the electrocatalyst. Platinum serves as the electrocatalyst, which
promotes the rate of electrochemical reactions (oxidation/reduction) for a given surface
area. The carbon black is also somewhat hydrophobic, depending on the surface
properties of the material. The composite structure of PTFE and carbon establishes an
extensive three-phase interface in the porous electrode, which is the benchmark of PTFE
bonded electrodes.

In MCFCs, which operate at relatively high temperature, no materials are known that
wet-proof, are retains porous structure against ingress by molten carbonates.
Consequently, the technology used to obtain a stable three-phase interface in MCFC
porous electrodes is different from that used in PAFCs. In the MCFC, the stable interface
is achieved in the electrodes by carefully tailoring the pore structures of the electrodes
and the electrolyte matrix (L1AIO2) so that the capillary forces establish a dynamic
equilibrium in the different porous structures. In a SOFC, there is no liquid electrolyte
present that is susceptible to movement in the porous electrode structure, and electrode
flooding is not a problem. Consequently, the three-phase interface that is necessary for
efficient electrochemical reaction involves two solid phases (solid/electrolyte/electrode)
and a gas phase. A critical requirement of porous electrodes for SOFC is that they are
sufficiently thin and porous to provide an extensive electrode/electrolyte interfacial
region for electrochemical reaction.
The essential criteria for a better electrode material are:

• high electronic conductivity

• high adsorption capacity of reactant and oxidant

166 Fuel Cells

• chemical and structural stability under the conditions employed in devices i.e.,
operating temperature, wide range of partial pressures of reactant and oxidant,
concentration of electrolyte

• chemical and thermomechanical compatibility to electrolyte and interconnector
materials

• high ionic conductivity

• ability to decompose the intermediate species formed during the
oxidation/reduction process

• tolerant to contaminants e.g., halide ions, NO x , CO x , SO x

• low cost of materials

Oxygen reduction reaction (ORR), which is a common cathodic reaction to all the fuel
cell devices, has been studied over the years because of its fundamental complexity, great
sensitivity to the electrode surface, and sluggish kinetics. The sluggish kinetics of ORR
under the conditions employed in electrochemical devices is due to the low partial
pressure of oxygen in air, slow flow rate of oxygen (i.e., less residence time for oxygen
molecules on active sites) under ambient conditions. The main disadvantage in this
important electrode reaction is the exchange current density (j ) value in the region of
10" 10 A/cm 2 in acidic medium and 10" 8 A/cm 2 at 298 K in alkaline solution which is lower
than the jo value of anodic reaction (10~ 3 A/cm 2 ) in all the electrochemical devices. Hence
(from the equation r\ = RT/nF ln(j/j )) the oxygen reduction reaction usually contributes
considerably to the overpotential and therefore results in a low efficiency in the
functioning of electrochemical energy devices using air as oxidant. Understanding and
exploitation of electrocatalysis for this reaction is needed more than any other reactions
in electrochemical devices. Oxygen undergoes a two-step indirect reduction reaction. On
most of the electrocatalysts, oxygen reduction takes place by the formation of high
energy intermediate, H2O2 followed by further reduction to H 2 0. The stable H2O2
intermediate is undesirable, as it lowers the cell voltage and H2O2 attacks and corrodes
the carbonaceous electrode material commonly used. Better catalysts are needed to speed
the decomposition of H2O2 to reduce its impact on the overall reaction. Similarly, a
catalyst can enhance the fuel dissociation rate at the anode. In order to obtain maximum
efficiency and to avoid corrosion of carbon supports and other materials by peroxide, it is

An Introduction to Energy Sources 167

desired to achieve a four electron reduction. Finding suitable electrocatalysts that can

promote the direct four electron reduction of oxygen molecule is an important task.

The characteristic features, advantages and limitations of various types of fuel cells are

given below.

5.1. Alkaline fuel cells (AFCs)

The first commercial fuel cell systems were the AFCs that became available in the 1950s.

AFCs were used to power the Apollo spacecrafts and are currently used in the Space

Shuttles. The electrolyte in AFCs is a concentrated KOH solution. For low temperature

applications (60-90 °C) the KOH concentration is 35-50 wt%. To achieve optimum

performance of AFCs with KOH concentrations of 85 wt% the operating temperature was

increased to 200 °C. These high temperature cells are also operated at high pressures (4-6

atm) to prevent the electrolyte solution from boiling.

Pure H2 and O2 are input as the fuel and oxidizer in an AFC. The gas diffusion electrodes

are constructed of porous carbon and are doped with Pt to catalyze the oxidation and

reduction reactions. The anodes contain 20% Pd in addition to the Pt and the cathodes

contain 10% Au and 90% Pt. For higher temperature operations, Ni catalysts are also

used. Ni is used for the inter connectors in an AFC stack. The AFC operates at up to ~1

A/cm 2 at 0.7 V.

The mobile ions in the system are the OH" ions in the alkaline solution that are

transported from the cathode, where reduction of O2 occurs, to the anode, where

oxidation of H2 occurs. Water is produced at the anode. The following reactions define

the operation of AFCs:

At anode: H 2 + 2 OH"^ 2 H 2 + 2 e"

At cathode: V* 2 + H 2 + 2 e" -> 2 OH"

Cell reaction: H 2 + l A 2 -> H 2

Although AFCs have the highest electrical efficiency of all fuel cell systems (60% LHV),

they are extremely sensitive to impurities. The presence of N 2 and impurities in the gas

streams substantially reduce the cell efficiency. The presence of even small amounts of

CO2 is detrimental to the long-term performance of AFCs because K2CO3 forms and

inhibits gas diffusion through the carbon electrodes. The small amounts of CO2 in air

(-300 ppm) preclude the use of air as the oxidant in an AFC. This restriction limits the

168 Fuel Cells

use of these fuel cell systems to applications such as space and military programs, where
the high cost of providing pure H 2 and O2 is permissible. Because pure gases are used,
AFCs can generate pure, potable water for consumption during space missions.
5.2. Phosphoric acid fuel cells (PAFCs)

Other than the AFCs, PAFCs are closer to commercialization than other fuel cell systems.
The two intended commercial uses for PAFCs are 1) distributed power using reformed
natural gas as a fuel; and 2) for small-scale, on-site cogeneration. Air is used as the
oxidant. In contrast to the AFC, PAFCs are tolerant of CO2 because concentrated
phosphoric acid (H3PO4) is used as the electrolyte. Compared to other inorganic acids,
phosphoric acid has relatively low volatility at operating temperatures of 150-220 °C.
Protons migrate from the anode to the cathode through 100% H3PO4 that is immobilized
in a SiC-poly(tetrafluoroethylene) matrix. Electrodes are made of platinized, gas
permeable graphite paper. The water produced at the cathode is removed with the excess
O2 and the N2. PAFCs have demonstrated excellent thermal, chemical, and
electrochemical stability compared to other fuel cell systems. PAFCs are defined by the
following reactions:
At anode: H 2 ^2H + +2e"
At cathode: Vi 2 + 2 H + + 2 e" -+ H 2
Cell reaction: H 2 + Vi 2 -> H 2

To optimize the ionic conductivity of the electrolyte, operating temperatures are
maintained between 150-220 °C at pressures ranging from atmospheric to ~8 atm.
Reduction of oxygen is slower in an acid electrolyte than in an alkaline electrolyte, hence
the need for Pt metal in the electrodes to help catalyze the reduction reactions. CO
poisoning of the Pt electrodes is slower at PAFC operating temperatures than at lower
temperatures so up to 1% CO in the fuel gas produced during the reforming process can
be tolerated. At lower temperatures CO poisoning of the Pt in the anode is more severe.
Currently, Pt based materials were used as anode and cathode. The anode operates at
nearly reversible voltage with ~0.1 mg/cm 2 catalyst loading. The cathode requires a
higher catalyst loading of ~1 mg/cm 2 of catalyst. PAFCs are already semicommercially
available in container packages (200 kW) for stationary electricity generation. Hundreds
of units have been installed all over the world.

An Introduction to Energy Sources 169

Aside from the CO produced during hydrocarbon reforming, the concentration of other
impurities must be low compared to the reactants and diluents. Sulfur gases (mainly H2S
and COS) that originate from the fuel gas can poison the anode by blocking active sites
for H 2 oxidation on the Pt surface. Molecular nitrogen acts as a diluent but nitrogen
compounds like NH3, HCN, and NO x are potentially harmful impurities. NH3 acts as a
fuel, however, the oxidant nitrogen compounds can react with the H3PO4 to form a
phosphate salt, (NH4)H2P04. Unacceptable performance losses can occur if the
concentration of this phosphate salt in the electrolyte increases above 0.2 mole%.
5.3. Proton exchange membrane fuel cells (PEMFCs)

PEM fuel cells are a serious candidate for automotive applications, but also for small-
scale distributed power generation, and for portable power applications as well. PEMFCs
contain a proton conducting ion exchange membrane as the electrolyte material. The
membrane material is a fluorinated sulfonic acid polymer commonly referred to by the
trade name given to a material developed and marketed by DuPont - Nation®. The acid
molecules are immobile in the polymer matrix; however, the protons associated with
these acid groups are free to migrate through the membrane from the anode to the
cathode, where water is produced. The electrodes in a PEMFC are made of porous carbon
cloths doped with a mixture of Pt and Nation®. The catalyst content of the anode is ~0.1
mg/cm 2 , and that of the cathode is ~0.5 mg/cm 2 . The PEMFC operates at ~1 A/cm 2 at 0.7
V.

PEMFCs use H2 as the fuel and O2 as the oxidant. The PEMFC is insensitive to CO2 so
air can be used instead of pure O2 and reforming hydrocarbon fuels can produce the H 2 .
Thermally integrating fuel reformers with operating temperatures of 700-800 °C with
PEMFCs that operate at 80 °C is a considerable challenge. The PEMFC is defined by the
following reactions:
At anode: H 2 ^2H + +2e"
At cathode: Vi 2 + 2H + +2e"^ H 2
Cell reaction: H 2 + Vi 2 -> H 2

PEMFCs have received considerable attention lately as the primary power source in
electric vehicles for several reasons. Since the electrolyte is a polymeric material, there is
no free corrosive liquid inside the cell (water is the only liquid), hence material corrosion

170 Fuel Cells

is kept to a minimum. PEMFCs are also simple to fabricate and have a demonstrated long
life. On the other hand, the polymer electrolyte (Nation®) is quite expensive and Pt
loadings in the electrodes are quite high so the fuel cell cost is high. The power and
efficiency of a PEMFC is also dependent on the water content of the polymer electrolyte,
so water management in the membrane is critical for efficient operation. The conductivity
of the membrane is a function of the number of water molecules available per acid site
and if the membrane dries out, fuel cell power and efficiency decrease. If water is not
removed from the PEMFC the cathode can become flooded which also degrades cell
performance. For high temperature PEMFCs, polybenimidazole based membranes will be
preferred.

The required moisture content of the membrane is what limits the operating temperature
of a PEMFC to less than 120 °C. This temperature ensures that the by-product water does
not evaporate faster than it is produced. Low operating temperatures equates to high Pt
loadings in the electrodes to efficiently catalyze the oxidation and reduction reactions.
The Pt content of the electrodes also necessitates that the CO content of the fuel gas be
very low (< 5 ppm) because CO blocks the active sites in the Pt catalyst. Therefore, if a
hydrocarbon reformer is used to produce H 2 , the CO content of the fuel gas needs to be
greatly reduced. This is usually accomplished by oxidation of CO to CO2, using a water
gas shift reactor, or using pressure swing adsorption to purify the hydrogen.
5.4. Direct methanol fuel cells (DMFCs)

The DMFC uses the same basic cell construction as for the PEMFC. It has the advantage
of a liquid fuel in that is easy to store and transport. There is no need for the reformer to
convert the hydrocarbon fuel into hydrogen gas. Methanol is the liquid fuel having high
energy density (6.2 kWh/kg) among all the liquid fuels and next to hydrogen. The anode
feedstock is a methanol and water mixture or neat methanol, depending on cell
configuration. The DMFC is under development as a power source for portable electronic
devices such as notebook computers and cellular phones. The pure methanol or a
methanol-water mixture would be stored in a cartridge similar to that used for fountain
pens. Refueling would involve the quick replacement of the cartridge. The reaction for
the direct conversion of methanol has a similar voltage as for hydrogen.

An Introduction to Energy Sources 171

DMFCs use CH3OH as the fuel and O2 as the oxidant. Due to the chemical similarity of
water and methanol, the methanol has considerable solubility in the polymer membrane,
leading to significant crossover from the anode side to the cathode side of the cell. On
reaching the cathode, the methanol is oxidized. This significantly lowers the cathode
voltage and the overall efficiency of cell operation. The typical DMFC yields ~0.5 V at
400 mA/cm 2 at 60 °C. The DMFC is defined by the following reactions:
At anode: CH 3 OH + H 2 -> C0 2 + 6 H + + 6 e"
At cathode: 3/2 2 + 6 H + + 6 e" -> 3 H 2
Cell reaction: CH 3 OH + 3/2 2 -> C0 2 + 2 H 2

The main disadvantage of the DMFC system is the relative low power density, which has
to be significantly improved if the DMFC should be a viable alternative to the PEMFC
plus reformer system. The lower cell performance of a DMFC is caused by the poor
kinetics of the anode reaction. The oxidation reaction proceeds through the formation of
carbon monoxide as an intermediate which strongly adsorbs on the surface of a Pt
catalyst. Therefore, a potential, which is more anodic than the thermodynamic value, is
needed to obtain a reasonable reaction rate. In contrast to the PEMFC, where it is mainly
the cathode that is kinetically hindered, both electrodes of a DMFC suffer from kinetic
losses. Consequently, numerous materials were studied to find an electrode material that
displays an enhanced catalytic activity and therefore lower overpotentials towards the
methanol oxidation. At present, the most active anode catalysts are based on Pt-Ru
alloys. Ruthenium reduces the poisoning effect by lowering the overpotentials at the
anode and thus increases considerably the catalytic activity of pure platinum. The
platinum-ruthenium catalyst loadings for the anode are higher than for the PEMFC and
are in the range of 1-3 mg/cm 2 . Cathode catalysts are based on Pt and Pt alloys (Pt-M
where M = Cr, Co, Fe and Ni).
5.5. Molten carbonate fuel cells (MCFCs)

MCFCs contain an electrolyte that is a combination of alkali (Li, Na, and K) carbonates
stabilized in a LiA10 2 ceramic matrix. The electrolyte should be pure and relatively free
of alkaline earth metals. Contamination by more than 5-10 mole % of CaCC>3, SrCC>3, and
BaC03 can lead to performance loss. Electrons are conducted from the anode through an
external circuit to the cathode and negative charge is conducted from the cathode through

172 Fuel Cells

the electrolyte by CO3 2 ~ ions to the anode. Water is produced at the anode and removed
with CO2. The CO2 needs to be recycled back to the fuel cell to maintain the electrolyte
composition. This adds complexity to the MCFC systems. The oxidation and reduction
reactions that define MCFC operation are as follows:
At anode: H 2 + C0 3 2 " "^ H 2 + C0 2 + 2 e"

CO + C0 3 2 ""^C0 2 +2e-
Shift: CO + H 2 -> H 2 + C0 2
At cathode: l A 2 + C0 2 + 2 e" -> C0 3 2 ~
Cell reaction: H 2 + V2 2 -> H 2

MCFCs typically operate at temperatures between 600-700 °C providing the opportunity
for high overall system operating efficiencies, especially if the waste heat from the
process can be utilized in the fuel reforming step or for cogeneration. Operating
temperatures higher than 700 °C lead to diminishing gains in fuel cell performance
because of electrolyte loss from evaporation and increased high temperature materials
corrosion. Typical operating parameters are ~150 mA/cm 2 at 0.8 V at 600 °C.
The high operating temperature of a MCFC system also provides for greater fuel
flexibility; a variety of hydrocarbon fuels (natural gas, alcohols, landfill gas, syn gas from
petroleum coke, coal and biomass, etc.) can be reformed to generate hydrogen for the fuel
cell. The CO from biomass and coal gasification product gas and reformed hydrocarbons
is not used directly as a fuel but when mixed with water vapor can produce additional
hydrogen via the water-gas shift reaction. Oxygen or air is used as the oxidant. An
attractive design incorporates an internal fuel reformer within the fuel cell eliminating the
need for a separate fuel processor.

A higher operating temperature also means that less expensive materials can be used for
the electrocatalysts in the electrodes; Pt is not required and Ni is used as the catalyst. The
Ni in the cathode becomes oxidized and lithiated (from contact with the electrolyte)
during initial operation of a MCFC so that the active material is Li-doped NiO.
Unfortunately, NiO is soluble in molten carbonates leading to the possible dissolution of
the cathode and dispersion of metallic nickel in the electrolyte, which can eventually
short-circuit the electrodes. This is one of the materials issues that is being investigated to

An Introduction to Energy Sources 173

improve the long-term operability of MCFC systems. Recently, LiCo0 2 and Li2Mn03
were found to be alternative materials as cathode.

The anode contains Ni doped with 10% Cr to promote sintering. An external methane
reformer is not needed in a MCFC system because the presence of Ni in the anode at
MCFC operating temperatures is very effective for internal CH4 reforming at the anode.
Internal methane reforming can increase overall system efficiencies, but can also induce
unwanted temperature gradients inside the fuel cell that may cause materials problems.
Catalyst poisoning is also an issue if the sulfur content of the reagent gases is greater than
10 ppm, similar to all Ni-based fuel-reforming systems. Coke formation on the anode
from fuel reforming can also be an issue.
5.6. Solid oxide fuel cells (SOFCs)

SOFC systems operate between 900-1000 °C, higher than any other fuel cell system. At
these operating temperatures, fuel composition is not an issue because in the presence of
enough water vapor and oxygen complete oxidation will be achieved, even in the absence
of catalytic materials. High overall system efficiencies are possible with waste heat
recovery. The electrolyte material in a SOFC is yttrium (8-10 mol%) stabilized zirconia
(YSZ). This material is a solid with a stable cubic structure and very high oxide
conductivity at SOFC operating temperatures. The mobile O 2 " ions migrate from the
cathode to the anode where water is produced. The electrochemical reactions occurring in
a SOFC system are as follows:
At anode: H 2 + O 2 " — ► H 2 + 2 e"
At cathode: V2 2 + 2e~-> O 2 "
Cell reaction: H 2 + l A 2 -> H 2

Similar to the MCFC systems, the high operating temperatures of the SOFCs provides
fuel flexibility without the need for expensive catalysts in the electrodes. The cathode in a
SOFC consists of mixed oxides with a perskovite crystalline structure, typically Sr-doped
lanthanum manganate (LaMnOs). The anode material is a Ni cermet (ceramic and metal
composite). It contains metallic Ni for catalytic activity in an YSZ support. The YSZ
adds mechanical, thermal, and chemical stability, chemical and thermal compatibility
between the anode and the electrolyte is not an issue. Like the MCFC systems, internal

174 Fuel Cells

methane steam reforming at the Ni-based anode in the presence of water vapor is possible
in SOFC systems. The cells operate at ~1 A/cm 2 at 0.7 V.

Overall, SOFC systems can tolerate impurities because of their high operating
temperatures. Sulfur tolerances can be up to two orders of magnitude higher in SOFCs
than in other fuel cell systems because of the high operating temperatures. Energy
efficient, high temperature sulfur removal methods are used to lower the sulfur content of
the gas to less than 10 ppm. At the same time, the high operating temperatures of SOFCs
can cause considerable materials issues like material incompatibilities (thermal and
chemical) and corrosion.

Significant research and development efforts have gone into technically and cost-
effectively addressing materials issues in SOFC systems for commercial applications.
This is reflected in the variety of designs for SOFC systems. There are three general types
of designs for SOFC systems: tubular, bipolar monolithic, and bipolar planar. The bipolar
designs have a bipolar plate that prevents reactant gases in adjacent cells from mixing and
provides serial electrical interconnectivity between cells. The single cells are stacked with
interconnectors, gas channels, and sealing elements in between. There are two types of
tubular designs: seal-less and segmented cell in-series. A single cell in a tubular SOFC
consists of a long porous YSZ ceramic tube that acts as a substrate. The cathode,
followed by the electrolyte, and finally the anode are deposited on the outer surface of the
tube. A portion of the tube is left with a strip of the cathode covered by the interconnector
material to make the electrical connection. Individual tubes are arranged in a case and air
flows inside the tubes while fuel flows around the outside of the tubes.
Developments in SOFC systems that operate at intermediate temperatures (550-800 °C)
are currently receiving considerable attention. Reducing the operating temperature of
SOFC systems is being pursued in an attempt to reduce the cost of these systems. Some
of the benefits of a reduced operating temperature include: better thermal integration with
fuel reformers and sulfur removal systems, reduced material issues such as less thermal
stress and more material flexibility, lower heat loss, shorter time to achieve operating
temperature, and less corrosion. Capitalizing on the benefits of lower SOFC operating
temperatures is an area of continued and future research and development.

An Introduction to Energy Sources 175

References

1. B. Viswanathan and M. Aulice Scibioh, Fuel Cells - Principles and Applications,
Universities Press (India) Private Limited, 2006.

2. W. Vielstitch, Fuel Cells, Wiley/Interscience, London, 1965.

3. K. Kordesch and G. Simader, Fuel Cells and their Applications, VCH, Weinheim,
Germany 1996.

4. L. Carrette, K. A. Friedrich and U. Stimming, Fuel Cells 1 (2001) 1.

5. M. Winter and R. J. Brodd, Chem. Rev. 104 (2004) 4245.

6. W. Vielstich, H. Gasteiger and A. Lamm. (Eds), Hand book of Fuel Cells -
Fundamentals, Technology and Applications, Vol. 2: Electrocatalysis, John Wiley &
Sons, Ltd, 2003.

Chapter- 10
SUPERCAPACITORS

T. Meialagan

1. Introduction

Supercapacitors have received considerable attention due to their remarkable properties,
specifically higher cyclability and power density in comparison with batteries, and higher
energy density in comparison with common capacitors. Supercapacitors are electrical
storage devices that can deliver a higher amount of energy in a short time. Hybrid-electric
and fuel-cell powered vehicles need such a surge of energy to start, more than can be
provided by regular batteries. Supercapacitors are also needed in a wide range of
electronic and engineering applications, wherever a large, rapid pulse of energy is
required. Capacitors which store the energy within the electrochemical double-layer at
the electrode/electrolyte interface are known under various names which are trade marks
or established colloquial names such as 'double-layer capacitors', 'supercapacitors',
'ultracapacitors', 'power capacitors', 'gold capacitors' or 'power cache'.
'Electrochemical double-layer capacitor' is the name that describes the fundamental
charge storage principle of such capacitors. However, due to the fact that there are in
general additional contributions to the capacitance other than double layer effects, these
capacitors are termed as electrochemical capacitors (EC).

Electrochemical capacitors have been known since many years. First patents date back to
1957 where a capacitor based on high surface area carbon was described by Becker. Later
in 1969 first attempts to market such devices were undertaken by SOHIO. However, only
in the nineties electrochemical capacitors became famous in the context of hybrid electric
vehicles. A DOE ultracapacitor development program was initiated in 1989, and short
terms as well as long term goals were defined for 1998-2003 and after 2003,
respectively. The EC was supposed to boost the battery or the fuel cell in the hybrid
electric vehicle to provide the necessary power for acceleration, and additionally allow
for recuperation of brake energy. Today several companies such as Maxwell
Technologies, Siemens Matsushita (now EPCOS), NEC, Panasonic, ELNA, TOKTN, and
several others invest in electrochemical capacitor development. The applications

An Introduction to Energy Sources

177

envisaged principally boost the components supporting batteries or replacing batteries
primarily in electric vehicles. In addition alternative applications of EC not competing
with batteries but with conventional capacitors are coming up and show considerable
market potential. Such applications will also be discussed in detail. The reason why
electrochemical capacitors were able to raise considerable attention is visualized in Fig. 1
where typical energy storage and conversion devices are presented in the so called
'Ragone plot' in terms of their specific energy and specific power. Electrochemical
capacitors fill in the gap between batteries and conventional capacitors such as
electrolytic capacitors or metallized film capacitors. In terms of specific energy as well as
in terms of specific power this gap covers several orders of magnitude.

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Fig. 1 . Sketch of Ragone plot for various energy storage and conversion devices. The
indicated areas are rough guide lines.

2. Principle of operation

In a conventional capacitor (condenser), the charge accumulation is achieved
electrostatically by positive and negative charges residing on two interfaces separated by
a vacuum or a molecular dielectric (a film of mica, a space of air, or an oxide film).
Supercapapcitors store the electric energy in an electrochemical double layer formed at
the interface between the polarizable electrodes and compensate for the electronic
charges at the electrode surface, as shown in Figure 2. This charge distribution layer is
called the electric double layer (or electrochemical double layer). Figure 2 presents the
principle of an electrochemical capacitor.

178

Supercapacitors

Electrolyte, Separator

Carbon p&rtictes in
contact wilt) an

electrolyte Film

Charged

Electrolyte

Fig. 2. (A) Principle of a single-cell double-layer capacitor and illustration of the potential
drop at the electrode/electrolyte interface (B) Function of carbon electrode in an
electrochemical capacitor

The thickness of the double layer depends on the concentration of the electrolyte and on
the size of the ionic clusters and is typically of the order of 5- 10 A for concentrated
electrolytes. The capacitance, C, accumulated in the electric double layer formed at the
interface between the polarizable electrodes and the electrolyte solution is defined by

C=s/4 7id5J dS

Where s is the dielectric constant of the electrolyte, S is the distance from the electrode
interface to the center of the ion, and S is the surface area of the electrode interface. The
corresponding electric field in the electrochemical double layer is high and is assumed to
be 10 V/cm. Compared to conventional capacitors where a total capacitance is typically
on the order of pico-farads and microfarads, the capacitance and the energy density stored

An Introduction to Energy Sources 179

in the supercapacitor by the electrochemical double layer is higher. To achieve a higher
capacitance the surface area of the electrode is additionally enlarged by using porous
electrodes, where an extremely large internal surface area is expected.

There are several techniques for determining the specific capacitance, such as a unit cell
test (two electrode system), a half cell test (three electrode system), and an impedance
test. The unit cell and half-cell tests are mainly used to determine the specific
capacitance of the supercapacitor. The specific capacitances reported in the literature are
not consistent, mainly due to the experimental methods used to determine them. For the
sake of consistency, it is worth specifying the electrochemical technique for calculating
the specific capacitance between the two electrode and three electrode systems. Figure 3
shows the double layer of electrodes used in the two-electrode system (2E), which
represents a real double layer supercapacitor device and its equivalent circuit. Figure 3 b
shows the double layer of electrodes used in the three-electrode system (3E), which is
used in the laboratory cell with a reference electrode and its equivalent circuit. Assuming
that the weight of each individual electrode is m, then Ci=C2=C. The capacitance
measured for the two electrode system is C2e=1/2C. The specific capacitance turns out to
be C sp ec- 2E= C2E /{2m) =l/4{C/m). However, for the three electrode system, the double
layer capacitance measured is C 3E =C and the specific capacitance is C spec .3 E = C 3E / (m)
=(C/m).Thus the relationship between the specific capacitance measured with the two
electrode and three electrode techniques is C spec .3E=4 C spec . 2E

In the double layer at plane electrodes, charge densities of about 16-50 |jF/cm 2 are
commonly realized. Taking an average value of 30 (iF/cm 2 , the capacitance of a single
Polarisable electrode with a typical surface area of 1000 m 2 /g for porous materials leads
to a specific capacitance 300 F/g. At 1 V in an aqueous electrolyte, the maximum storage
energy, E, is E=CV?/2= (300 X 1 2 )/2=150 W-s/g, 150kJ/kg or 42 W-h/kg, theoretically.
This value is considerably lower than that obtained for available batteries but higher than
that for conventional capacitors. It should be mentioned that the above value depends on
the double layer capacitance, the specific surface area of the respective electrode
material, the wetting behaviour of the pores and the nominal cell voltage.

180

Supercapacitors

I ©

c-
©
-

Reference

(a)

tb)

Fig. 3. Electric double layer and its equivalent circuit in (a) two-dimensional electrode
system and (b) three -electrode system

The maximum power density of a supercapacitor is given by P max =Vi 2 /4R [V;= initial
voltage, R= equivalent series resistance (ESR)]. Therefore, the key factors determining
the power of supercapacitors are the resistivity of the electrode itself, the resistivity of the
electrolyte within the porous layer of electrode, and the contact resistance between the
electrode and the current collector, as shown in Fig 4.

electrode current

material collector

I i

Fig.4. Equivalent circuit of an electrochemical capacitor
In evaluating the performance of supercapacitors, the characterization of their energy
density and power density are the most important factors of rating electrochemical power

An Introduction to Energy Sources

181

devices. In addition, from practical and fundamental points of view, there is a question of
how the energy density and power density are related to various types of electrochemical
power sources, including fuel cells and rechargeable batteries.
3. Differences between a Supercapacitor and Battery

The most important difference between a supercapacitor and a battery is the principle of
electrochemical energy storage. Electrochemical energy can be stored in two
fundamentally different ways. In a battery, the potentially available chemical energy
storage requires Faradaic oxidation and reduction of electrochemically active reagents to
release charges that can perform electric work when they flow between two electrodes
having different potentials; that is, the charge storage is achieved by electron transfer that
produces a redox reaction in the electroactive material according to Faraday's law.

Table 1. Advantages and disadvantages of supercapacitor energy storage devices

Advantages

Disadvantages

(1) Long cycle life , > 100,000 cycles

(2) Excellent power density , > 10 6 W/Kg

(3) Simple principle and mode of construction

(4) Combines state of charge indication

(5) Can be combined with secondary battery
for hybrid applications (electric vehicles)

(1) Limited energy density

(2) Poor volume energy density

(3) Low working voltage

(4) Requires stacking for high
potential operation (electric
vehicles)

With an electric double-layer capacitor (EDLC), the charge storage process is non -
Faradaic; that is, ideally, no electron transfer takes place across the electrode interface
and the storage of electric charge and energy is electrostatic. Actual electron charges are
accumulated on the electrode surface with lateral repulsion and involvement of redox
chemical changes. Table 1 summarizes the perceived advantages and disadvantages of
such EDLC energy storage. Because the charging and discharging of such EDLCs
involve no chemical phase and composition changes, such capacitors have a high degree
of cyclability on the order of 10 times and a high specific power density , although the
specific energy density is rather small. However in some cases of the supercapacitor
based on pseudocapacitance (redox type of supercapacitor), the essential process is

182

Supercapacitors

Faradaic; that is the charge storage is achieved by an electron transfer that produces a
redox reaction (Faradaic reaction) in the electroactive materials according to Faraday's
law. The supercapacitors based on pseudocapacitance have higher specific capacitance
than the EDLCs, due to the redox reaction as in a battery, although the redox reaction
gives rise to high internal resistance in supercapacitors, resulting in a decrease in specific
power density. The typical electrodes of supercapacitors based on pseudocapacitance are
metal oxides (i.e., RuC>2, I1O2, C03O4) and conducting polymers (i.e., Polypyrrole,
polyaniline, Poly thiophene).
Table 2. Overall comparison of supercapacitor and battery characteristics

Item

Supercapacitor

Battery

Slope of charge and discharge
curve

Declining slope

Constant slope

Intrinsic stage of charge
indication

Good

Bad

Energy density

Poor

Good

Power density

Good

Poor

Cyclability and cycle life

Excellent

Bad

Origin of internal IR

High area matrix +
electrolyte

Active electrode materials +
electrolyte

Life time

Long

Poor

Cell stacking by bipolar
system

Possible

Impossible

A supercapacitor requires two equivalent electrodes, one of which is charged negatively
with respect to the other, the charge storage and separation being electrostatic. At each
electrode, the charge storage and separation are established across the electrode interface.
Usually, the electrodes of supercapacitors have high surface area and porous matrices.
However, batteries have bipolar electrode configuration for high voltage series
combinations.

An Introduction to Energy Sources

183

For a battery, the maximum Gibbs energy is the product of charge Q and the difference
of potential, AE, between the Nernstian reversible potentials of the two electrodes, that is,
G= Q. AE. In the capacitor case, for a given charge Q, G is 1/2 QV. For a given electrode
potential difference, AE= V, it is evident that the energy stored by a two -electrode cell
accommodating a given Faradaic charge Q at voltage AE= V, is twice that stored in a
capacitor charged with the same Q at the same voltage. In the process of charging, a pure
electric double layer capacitor, every additional element of charge has to do electrical
work (Gibbs energy) against the charge density already accumulated on the electrodes,
progressively increasing the interelectrode potential difference.

ft.

charge
■■--* ■*

Battery

■> *•

discharge

charge

discharge

Time

Fig. 5. Difference in discharge and recharge relationships for a supercapacitor and a
battery

In a battery cell being charged, a thermodynamic potential (ideally) exists independent of
the extent of charge Q added, as long as two components (reduced and oxidized forms) of
the electroactive material remain existing together. Thus, the potential difference
(electromotive force) of the battery cell is ideally constant throughout the discharge or
recharge half cycles, so that G= Q. AE rather than Q, 1/2 AE (or 1/2 V). This difference
can be illustrated by the discharge curves shown schematically in Fig. 5, where the
voltage in the capacitor declines linearly with the extent of charge, while that for an ideal
battery it remains constant as long as two phases remain in equilibrium. The decline in
the supercapacitor voltage arises formally since C=Q/V or V= Q/C; therefore,

184 Supercapacitors

dV/dQ=l/C. The ideal battery cell voltages on discharge and recharge, as a function of
state of charge, are shown as parallel lines of zero slope in Fig. 5. In the slope of the
discharge and recharge lines for the supercapacitor in Fig. 5, there is significant J R drop,
depending on the discharging and recharging rates. An overall comparison of
electrochemical capacitor and battery characteristics is given in Table 2.
4. Componenets of a Supercapacitor

A. Electrolyte

The electrolyte can be of solid state, organic or aqueous type. Organic electrolytes have a
very high dissociation voltage of around 4 V where as aqueous electrolytes (KOH or
H2SO4) has a dissociation voltage of around 1 V. Thus for getting an output of 12 V,
using aqueous electrolyte one would require 12 unit cells where as with organic
electrolyte one would require 3 unit cells. This clearly shows that for high voltage
requirement one should opt for organic electrolyte. There is added requirement using
organic electrolyte, as ions of organic electrolyte are larger, they require large pore size
of electrode material.

B. Separator

The type of separator depends upon the type of electrolyte used. If the electrolyte is
organic then polymer or paper separator are used. If the electrolyte is aqueous then
ceramic separators are used.

C. Electrode

As the energy storage capacity is directly proportional to the surface area of the electrode,
electrochemical inert material with high surface area are used. The common electrode
materials are metal oxides, Nanoporous carbon and graphite. Carbon based electrode can
be made of activated carbon, carbon fibers, carbon black, active carbon, carbon gel,
skeleton carbon or mesocarbon. Carbon electrode has very high surface area (as high as
3000 m 2 /gm). Recent work has explored the potential of carbon nanotubes as
electrode material.

5. Electrode materials for supercapacitors
5.1. Metal oxides:

An Introduction to Energy Sources 185

The concept and use of metal oxide as an electrode material in electrochemical capacitors
was introduced by Trassatti and Buzzanca based on ruthenium dioxide (RuCh) as a new
interesting electrode material. Some other oxides, such as, IrC>2, C03O4, M0O3, WO3 and
Ti02, as electrode materials in electrochemical capacitors have been discovered
The cyclic voltammogram of the metal oxide electrodes has almost rectangular shape and
exhibits good capacitor behaviour. However, the shape of the cyclic voltammogram is not
a consequence of pure double-layer charging, but a consequence of the redox reactions
occurring in the metallic oxide, giving rise to the redox pseudo capacitance.
A very high specific capacitance of up to 750 F/g was reported for RuC>2 prepared at
relatively low temperatures. Conducting metal oxides such as RuC>2 or IrC>2 were the
favored electrode materials in early electrochemical capacitors used for space or military
applications. The high specific capacitance in combination with the low resistance
resulted in very high specific power. An energy density of 8.3 W-h/kg and a power
density of 30 kW/kg were achieved in a prototype 25 -V electrochemical capacitor but
only with RuC>2. x H2O material and electrolyte. These capacitors however turned out to
be too expensive.

A rough calculation of the capacitor cost showed that 90 % of the cost resides in the
electrode material. In addition, these capacitor materials are only suitable for aqueous
electrolytes, thus limiting the nominal cell voltage to 1 V. several studies have attempted
to take advantage of the material properties of such metal oxides at a reduced cost. The
dilution of the costly noble metal by the formation of perovskites was investigated by
Guther et al. Other forms of metal compounds such as nitrides were investigated by Liu
et al. However, these materials are not yet commercially available in the electrochemical
capacitor market.
5.2. Conducting polymers

The discovery of conducting polymers has given rise to a rapidly developing field of
electrochemical polymer science. Conducting polymers, such as polyacetylene,
polyaniline, polypyrrole, have been suggested by several authors for electrochemical
capacitors. The conducting polymers have fairly high electronic conductivities, typically
of magnitudes of 1-100 S/cm. The electrochemical processes of conducting polymers are
electrochemical redox reactions associated with sequential Lewis acid or Lewis base

186 Supercapacitors

production steps so that the polymer molecules are converted to multiply charged
structure through electrochemical Lewis-type reactions involving electron withdrawal or
electron donation. Therefore, the pseudo capacitance by Faradaic redox processes in
conducting polymer based electrochemical capacitors is dominant, although about 2-5 %
of double-layer capacitance is included in the total specific capacitance
Such polymer electrode materials are cheaper than RuC>2 or IrC>2 and can generate
comparably large specific capacitance. However, the polymer electrode materials do not
have the long term stability and cycle life during cycling, which may be a fatal problem
in applications. Swelling and shrinking of electro-active conducting polymers is well
known and may lead to degradation during cycling. Therefore, these electro active
conducting polymers are also far from being commercially used in electrochemical
capacitors.
5.3. Carbon

Carbon materials for electrochemical energy devices, such as secondary batteries, fuel
cells and supercapacitors, have been extensively studied. However, each type of
electrochemical energy device requires different physical properties and morphology. For
supercapacitors, the carbon material for the EDLC type must have (i) high specific
surface area, (ii) good intra and inter-particle conductivity in porous matrices, (iii) good
electrolyte accessibility to intrapore surface area, and (iv) the available electrode
production technologies. Carbons for supercapacitors are available with a specific surface
area of up to 2500 m 2 /g as powders, woven cloths, felts or fibers. The surface
conditioning of these carbon materials for supercapacitor fabrication is of substantial
importance for achieving the best performance, such as good specific surface area,
conductivity, and minimum self discharge rates.
5.4 Activated carbon

Carbons with high specific surface area have many oxygen functional groups, such as
ketone, phenolic, carbonyl, carboxylic, hydroquinoid, and lactone groups, introduced
during the activation procedure for enlarging the surface area. These oxygen functional
groups on activated carbons or activated carbon fibers give rise to one kind of
electrochemical reactivity, oxidation or reduction. Oxidation or reduction of the redox
functional groups shows pesudocapacitance, which amounts to about 5-10 % of the total

An Introduction to Energy Sources

187

realizable capacitance. However, the various surface functionalities in activated carbons
are one of the factors that increase the internal resistance (equivalent series resistance;
ESR) due to the redox reaction. Activated carbons are cheaper than metal oxides and
conducting polymers and they have larger specific surface than the others. Activated
carbon based supercapacitors have been commercialized for small memory backup
devices. However, activated carbons show lower conductivity than metal oxides and
conducting polymers, resulting in a large ESR, which gives smaller power density.

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Fig. 6. Pores before and after activation of carbon as observed by TEM

In addition, the observed specific capacitances of the carbon based supercapacitors are
about one-fourth the theoretical capacitance in spite of their high specific surface area,
which is attributed to the existence of micropores. This is a weak point of active carbons
as electrode materials in supercapacitors with high energy density and power density.
Activated carbons are famous for their surface areas of 1000 to 3000m 2 /g. Fig. 6 shows
an observation with a TEM (Transmission Electron Microscope) magnified to 2,000,000
times using phase-contrast method. In the upper photo, each black line identifies a
graphite layer with the space between two adjacent lines measuring 0.34 nano-meters.
After activation as shown in the lower picture, the space has swollen to make the surface
area for double layer.

188 Supercapacitors

6. Carbon nanotube (CNT) based supercapacitors

During the last decade, the application of activated carbons as the electrode materials in
supercapacitors has been intensively investigated because of their high specific surface
area and relatively low cost. Since the specific capacitance of a supercapacitor is
proportional to the specific surface area, the effective surface area of the electrode
materials is important. Theoretically, the higher the specific surface area of an activated
carbon, the higher the specific capacitance should be. Unfortunately, the theoretical
capacitance of the activated carbons is not in good agreement with the observed value,
because of significant part of the surface area remains in the micropores (< 20A°), which
are not accessible to the electrolyte ions. Therefore, the pore size distribution together
with the surface area is important for the determination of the electric double layer
capacitance. From this point of view, carbon nanotubes have several advantages as the
electrode materials for supercapacitors. CNTs have a narrow distribution of mesopores
sizes, highly accessible surface area, low resistivity, and high stability, attracting great
interest world wide for building supercapacitors.
6.1 Carbon nanotube electrodes

In recent years, high power supercapacitors based on the CNT electrodes using aqueous
electrolytes have been reported. , Niu et al .have reported that supercapacitor electrodes,
prepared from catalytically grown multiwalled CNTs whose surface area is 430 m 2 /g,
show a maximum specific capacitance of 1 13 F/g and a power density of 8 kW/kg at an
energy density of 0.56 Wh/kg in a solution of 38 wt. % H2SO4 used as the electrolyte. Ma
et al, also used CNT electrodes based on CNTs that were prepared as in previous
publications but with a binder introduced to form solid electrodes. They obtained specific
capacitances of 15±25 F/g in a solution of 38 wt. % H2SO4. Frackowiak et al,
investigated the electrochemical characteristics of supercapacitors built from MWNT
electrodes with the specific surface area of 430 m 2 /g, in 1 M KOH aqueous solution as
well as the correlation of micro texture with the elemental composition of the materials.
They argued that the presence of mesopores due to the central canal and or the
entanglement of CNTs are the reasons for the easy access of the ions to the
electrode/electrolyte interface for charging the electric double layer. They detected pure
electrosatatic attraction of ions as well as quick Faradaic reactions upon varying surface

An Introduction to Energy Sources 189

functionality, which was induced during acidic oxidation. The values of specific
capacitance varied from 4 to 135 F/g, depending on the type of nanotubes and their post
treatments (acidic oxidation).

Zhang et al. studied supercapacitors using MWNT electrodes in organic electrolyte
systems. The MWNT electrodes exhibited a specific surface area of 100 m /g and a
measured specific capacitance of up to 18.2 F/g (16.6 F/cm 3 ) with 1M LiOC>4 in a
mixture of ethylene carbonate and propylene carbonate (1:1 volume ratio) as the organic
electrolyte solution. They found that the specific capacitance was lower than that reported
by other groups using aqueous electrolytes, due to the low specific surface area of the
MWNT electrode and the organic electrolyte solution used. However, the energy density
of the supercapacitor can reach 20 Wh/Kg at 10 mA discharge current density, depending
on the organic electrolyte solution system. The relative volume of mesopores and
macropores of the used electrode exceeds 92 % and micropores are nearly negligible. In
the case of the organic electrolytes, because of their large molecular structures, only
mesopores and macropores are accessible and are larger than those of activated carbons
for supercapacitors.

Since the sizes of hydrated ions are in the range of 6±7.6 A the minimum effective pore
size should be greater than 15 A °. It is known that, in general, pore sizes in the range of
30±50 A° are required to maximize the capacitance in the electrical double-layer
capacitor. In macropores (> 50 A .) the hydrated ions are usually loosely bound to the
surface layer and do not particularly contribute to the capacitance.

Fig. 7a shows the specific capacitances of the heat-treated electrodes at various
temperatures as a function of the charging time. Capacitances increase abruptly and reach
about 80 % of the maximum capacitance during the initial 10 min, regardless of the heat-
treatment temperatures. The capacitances gradually increase further and saturate to the
maximum values at long charging times. Persistent increase of the capacitance over a
long time is generally observed from the porous electrodes and is attributed to the
existence of various forms of pores and pore diameters in the electrode. The saturated
capacitance increases with increasing heat-treatment temperatures and saturates to 180
F/g at 1000 C. High- temperature annealing of CNT electrodes improves the quality of

190

Supercapacitors

the sample not only by increasing the specific surface area but also by redistributing the
CNT pore sizes to the smaller values near 30±50 A .

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Fig. 7. Electrochemical properties of the supercapacitor using the CNT electrodes, a) The
specific capacitances of the heat-treated electrodes at various temperatures as a function
of the charging time at a charging voltage of 0.9 V, where the capacitance was measured
at a discharging current of 1 mA/cm2. b) The specific capacitances of the heat-treated
electrodes at various temperatures as a function of the discharging current density at a
charging voltage of 0.9 V for 10 min. c) The cyclic voltammetric (CV) behaviors (sweep
rate, 100 mV/s) for the CNT electrodes at various heat- treatment temperatures, d) The
complex-plane impedance plots for the CNT electrodes for various heat-treatment
temperatures at an ac-voltage amplitude of 5 mV, Z 2 : imaginary impedance, Z0: real
impedance.

Fig. 7b shows the specific capacitance as a function of discharge current density at various
heat-treatment temperatures, where the data were taken from the samples charged at 0.9
V for 10 min. At low temperatures below 700 °C, the specific capacitance at a
discharging current density of 50 mA/m 2 drops by about 30 % of the capacitance at 1
mA/cm 2 . However, at high annealing temperature (1000 °C), the capacitance drops only
by about 10 % even for large discharging current density. The existence of the long flat
region in the discharging current density is of practical importance for applications of

An Introduction to Energy Sources 191

supercapacitors to various realistic devices. Large capacitance drops at low annealing
temperatures are caused by the internal resistance of the CNT electrode. Figure 7c shows
the cyclic voltammetric (CV) behavior with a sweep rate of 100 mV/s at various
temperatures. The inner integrated area (current x voltage) is the power density, which
increases with increasing heat- treatment temperatures. This power density will be larger
if the ESR, the slope of V/I (indicated by the dotted box in Fig. 7c), is smaller. The CV
curve at 1000 °C is close to the ideally rectangular shape, indicating the smallest ESR in
the CNT electrode. The magnitude of the ESR can be more clearly shown in the
complex-plane impedance plots, as shown in Fig. 7d. The electrolyte resistance, Rs, is
constant and varies with the electrolyte. The sum of the resistance of the electrode itself
and the contact resistance between the electrode and the current collector is represented
by Rf. The electrolyte resistance and the contact resistance are identical in all samples.
Therefore, a decrease of the Rf indicates a decrease of the CNT-electrode resistance. The
CNT electrode resistance decreases rapidly at high temperatures of 800 and 1000 °C. The
Rf is closely related to the power density, as evidenced by comparing two curves in
Figures 7c and 7d. The ideally polarizable capacitance will give rise to a straight line
along the imaginary axis (Z 2 ). In real capacitors with a series resistance, this line has a
finite slope, representing the diffusive resistivity of the electrolyte within the pore of the
electrode. With increasing heat-treatment temperature, the diffusive line comes closer to
an ideally straight line, as shown in Figure 7d. The formation of abundant pore diameters
of 30±50 A with increasing temperature may also enhance the diffusivity of the hydrated
ions in the pore, which in turn reduces the CNT-electrode resistance and increase the
capacitance.

6.2. Carbon nanotube-composite electrodes

To increase the capacitance of nanotubes, it is possible to increase the electrode surface
area or to increase the pseudo capacitance effects obtained by addition of special oxides
or electrically conducting polymers (ECP) like polypyrrole (PPy). The ECPs have the
advantage of lower costs compared to oxides. Another advantage is that the pseudo
capacitance effects of ECPs are quite stable. The modification of carbon material by a
specific additive providing quick pseudo-capacitance redox reactions is another way to
enhance capacitance. This is possible with metal oxides, but in this case the addition of

192

Supercapacitors

ECP is used. ECP itself has a capacitance of about 90 F/g. Pseudo capacitance effects of
ECP are relatively stable. If one can coat a nanotube with, for instance, polypyrrole the
profit of the good electronic conducting properties and keep the advantage of ionic
conductivity in the opened mesoporous network of the nanotube. These are perfect
conditions for a supercapacitor.

Frackowiak et al. took three types of electrically conducting polymers (ECPs), i.e.
polyaniline (PANI), polypyrrole (PPy) and poly-(3,4-ethylenedioxythiophene) (PEDOT)
have been tested as supercapacitor electrode materials in the form of composites with
multiwalled carbon nanotubes (CNTs).

Fig.8. SEM of composites from CNTs with PANI (a), PPy (b) and PEDOT (c) prepared
by chemical polymerization

In the case of polyaniline (Fig. 8a), the nanocomposite is homogenous and CNTs are
equally coated by conducting polymer. The average diameter of the PANI coated
nanotubes is up to 80 nm. By contrast, for the PPy composite (Fig. 8b) a globular
structure and irregular deposits are observed. In the case of the PEDOT/CNTs composite
a strong tendency for polymerization on the polymer itself appears.
The results of capacitance measurements on the different combinations of ECPs
composites working in their optimal potential range were also tested and are given in
Table 3. It can be concluded that the nanotubes with electrochemically deposited
polypyrrole gave a higher values of capacitance than the untreated samples.
Electrochemical behaviour of PANI dictates its choice as a positive electrode because of

An Introduction to Energy Sources

193

a rapid loss of conductivity in the negative potential range. On the other hand PPy as well
as PEDOT could serve as both electrodes (+) and (— ) taking into account a suitable
voltage range. Higher performance is observed for a PANI/CNTs (+)//PPy/CNTs (— )
capacitor which supplies 320 F g _1 . An additional increase of the supercapacitor power
and energy density through enhancement of the operating voltage can be easily realized
by application of activated carbon as a negative electrode. Instead of CNTs, acetylene
black could be also used as carbon additive in such composites; however, nanotubes act
as a more convenient backbone and allow a better dispersion of the conducting polymer.

Table 3. Combination of different materials for positive and negative electrodes of
supercapacitor

Positive (+)

Negative (-)

CCFg 1 )

U(V)

PANI

PPy

320

0.6

PANI

PEDOT

160

0.8

PANI

Carbon (PX21)

330

1.0

PPy

Carbon (PX21)

220

1.0

PEDOT

Carbon (PX21)

120

1.8

Electrolyte: 1 mol L ! H 2 S0 4 ; ECPs/CNTs composites (80 wt%/20 wt%)

7. Future of energy storage devices using carbon nanotubes

One of the important challenges is to realize optimal energy conversion, Storage and
distribution. These are clearly related to the development of several key technologies
such as transport, communications, and electronics. The environmental problems and
economic aspects related to the development and use of electrochemical energy storage
devices are of significance.

In particular, the new application and development of supercapacitors and Li-ion batteries
are directly related to technologies for manufacturing electric vehicles (EVs) and hybrid

194 Supercapacitors

electric vehicles (HEVs). The supercapacitor in EVs or HEVs will serve as short- time
energy storage device with high power density. It will also reduce the size of the primary
source (batteries (EVs), internal combustion engine (HEVs), fuel cell) and keep them
running at an optimized operation point. High power supercapacitors for EVs or HEVs
will require a high working voltage of 100 to 300 V with low resistance and large energy
density by series and parallel connections of elemental capacitors, in which very uniform
performance of each supercapacitor unit is essential.

Another prospect is the micro-supercapacitor and micro battery for use in micro- (or
nano)-electromechanical systems (MEMS or NEMS). In recent years MEMS (or NEMS)
technologies have attracted attention worldwide for their potential applications that
include medical communication equipment, sensors and actuators. Many technical
problems have to be solved for the successful development of these types of micro-
devices. One of the most important challenges is to develop an optimal micro-power
source for operating these devices. The MEMS (or NEMS) has, in many cases, low
current and power requirements. This may be realized by using Micro-supercapacitors
and micro batteries as power sources for these devices.
References

1. B. E. Conway, Electrochemical Supercapacitors, Kluwer Academic Publishers,
Norwell,MA(1999)

2. Y. H. Lee, K. H. An, J. Y. Lee, and S. C. Lim, 'Carbon nanotube-based
supercapacitors', Encyclopedia of Nanoscience and Nanotechnology, edited by H. S.
Nalwa, American Scientific Publishers, 625 (2004)

3. Y. H. Lee, K. H. An, S. C. Lim, W. S. Kim, H. J. Jeong, C. H. Doh, and S. I. Moon,
"Applications of carbon nanotubes to energy storage devices", New Diamond &
Frontier Carbon Technology 12(4), 209 (2002).

4. P. M. Wilde, T. J. Guther, R. Oesten, and J. Garche, J. Electroanal. Chem., 461, 154
(1999).

5. T.-C. Liu, W. G. Pell, B. E. Conway, and S. L. Robeson, J. Electrochem. Soc. 145,
1882(1998).

6. E. Frackowiak, K. Jurewicz, S. Delpeux, F. Beguin, J. Power Sources 97, 822 (2001).

7. E. Frackowiak, V. Khomenko, K. Jurewicz, K. Lota and F. Beguin,

An Introduction to Energy Sources 195

J. Power Sources 153, 413 (2006).

8. B. Zhang, J. Liang, C. L. Xu, B. Q. Wei, D. B. Ruan and D. H. Wu,
Mater. Lett, 51 539(2001).

9. C. Niu, E. K. Sichel, R. Hoch, D. Moy and H. Tennent,
Appl. Phys. Lett., 70, 1480 (1997).

10. R Z. Ma, J. Liang, B. Q. Wei, B. Zhang, C. L. Xu and D. H. Wu ,
J. Power Sources., 84, 126 (1999).

11. K. H. An, W. S. Kim, K. K. Jeon, Y. S. Park, J. M. Moon, S. C. Lim, D. J. Bae,

and Y. H. Lee, J. Electrochem. Soc, 149(8), A1058 (2002).

12. K. H. An, W. S. Kim, Y. C. Park, D. J. Bae, Y. C. Choi, S. M. Lee, D. C. Chung,
S. C. Lim, and Y. H. Lee, Adv. Mater., 13(7), 497 (2001).

Chapter -11

PHOTOVOLTAICS

M. Sathish

1. Introduction

Photovoltaic devices use semiconducting materials to convert sunlight directly into
electricity. It was first observed in 1839 by the French scientist Becquerel who detected
that when light was directed onto one side of a simple battery cell, the current generated
could be increased. In the late 1950s, the space programme provided the impetus for the
development of crystalline silicon solar cells. The first commercial production of
photovoltaic modules for terrestrial applications began in 1953 with the introduction of
automated photovoltaic production plants.

Conventional photovoltaic cells are made of crystalline silicon that has atoms arranged in
a three dimensional array, making it an efficient semiconductor. While this material is
most commonly used in converting light energy into electricity, it has associated
drawbacks, like high material costs for silicon, costly processes for purifying silicon and
manufacturing wafer, additional processes for assembly of modules, and bulky and rigid
nature of the photovoltaic panels.

2. How does this device work?

Photovoltaic cells convert sunlight directly into electricity without creating any air or
water pollution. Photovoltaic cells are made of at least two layers of semiconductor
material. One layer has a positive charge, the other negative. When light enters the cell,
some of the photons from the light are absorbed by the semiconductor atoms, freeing
electrons from the cell's negative layer to flow through an external circuit and back into
the positive layer. This flow of electrons produces electric current. To increase their
utility, many number of individual photovoltaic cells are interconnected together in a
sealed, weatherproof package called a module (Figure 1). When two modules are wired
together in series, their voltage is doubled while the current stays constant. When two
modules are wired in parallel, their current is doubled while the voltage stays constant.
To achieve the desired voltage and current, modules are wired in series and parallel into

An Introduction to Energy Sources

197

what is called a PV array. The flexibility of the modular PV system allows designers to
create solar power systems that can meet a wide variety of electrical needs, no matter
how large or small.

cell

♦♦♦

Fig.l. Photovoltaic cells, modules, panels and arrays

Photovoltaic modules are usually installed on special ground or pole mounting structures.

Modules may be mounted on rooftops provided that proper building and safety

precautions are observed. For more output, modules are sometimes installed on a tracker

- a mounting structure that moves to continually face the sun throughout the day.

The performance of photovoltaic modules and arrays are generally rated according to

their maximum DC power output under Standard Test Conditions (STC). Standard Test

Conditions are defined by a module operating temperature of 250 °C, and incident solar

irradiance level of 1000 W/m 2 and under Air Mass 1.5 spectral distribution. Since these

conditions are not always typical of how PV modules and arrays operate in the field,

actual performance is usually 85 to 90 % of the STC rating.

3. Fabrication of photovoltaic cells

3.1. Silicon based photovoltaic cells

The process of fabricating conventional single- and polycrystalline silicon photovoltaic

cells begins with very pure semiconductor-grade polysilicon - a material processed from

quartz and used extensively throughout the electronics industry. The polysilicon is then

198 Photovoltaics

heated to melting temperature, and trace amounts of boron are added to the melt to create
a p-type semiconductor material. Next, an ingot, or block of silicon is formed, commonly
using one of two methods: (1) by growing a pure crystalline silicon ingot from a seed
crystal drawn from the molten polysilicon or (2) by casting the molten polysilicon in a
block, creating a polycrystalline silicon material. Individual wafers are then sliced from
the ingots using wire saws and then subjected to a surface etching process. After the
wafers are cleaned, they are placed in a phosphorus diffusion furnace, creating a thin N-
type semiconductor layer around the entire outer surface of the cell. Next, an anti-
reflective coating is applied to the top surface of the cell, and electrical contacts are
imprinted on the top (negative) surface of the cell. An aluminized conductive material is
deposited on the back (positive) surface of each cell, restoring the p-type properties of the
back surface by displacing the diffused phosphorus layer. Each cell is then electrically
tested, sorted based on current output, and electrically connected to other cells to form
cell circuits for assembly in PV modules.
3.2 Band gap energies of semiconductors

When light shines on crystalline silicon, electrons within the crystal lattice may be freed.
But not all photons, only photons with a certain level of energy can free electrons in the
semiconductor material from their atomic bonds to produce an electric current. This level
of energy, known as the "band gap energy," is the amount of energy required to dislodge
an electron from its covalent bond and allow it to become part of an electrical circuit. To
free an electron, the energy of a photon must be at least as great as the band gap energy.
However, photons with more energy than the band gap energy will expend that extra
amount as heat when freeing electrons. So, it is important for a photovoltaic cell to be
"tuned" through slight modifications to the silicon's molecular structure to optimize the
photon energy. A key to obtaining an efficient PV cell is to convert as much sunlight as
possible into electricity.

Crystalline silicon has band gap energy of 1.1 eV. The band gap energies of other
effective photovoltaic semiconductors range from 1.0 to 1.6 eV. In this range, electrons
can be freed without creating extra heat. The photon energy of light varies according to
the different wavelengths of the light. The entire spectrum of sunlight, from infrared to
ultraviolet, covers a range of about 0.5 eV to about 2.9 eV. For example, red light has an

An Introduction to Energy Sources 199

energy of about 1.7 eV, and blue light has an energy of about 2.7 eV. Most PV cells

cannot use about 55 % of the energy of sunlight, because this energy is either below the

band gap of the material or carries excess energy.

3.3. Doping silicon to create n-Type andp-Type silicon

In a crystalline silicon cell, we need to contact p-type silicon with n-type silicon to create

the built-in electrical field. The process of doping, which creates these materials,

introduces an atom of another element into the silicon crystal to alter its electrical

properties. The dopant, which is the introduced element, has either three or five valence

electrons, which is one less or one more that silicon's four.

Phosphorous
atom

Normal f
bond

Extra
7~^ Unbound
! electron

Fig. 2. Phosphorus substituted n-type silicon

Phosphorus atoms, which have five valence electrons, are used in doping n-type silicon,
because phosphorus provides its fifth free electron. A phosphorus atom occupies the
same place in the crystal lattice formerly occupied by the silicon atom it replaces (Figure.
2). Four of its valence electrons take over the bonding responsibilities of the four silicon
valence electrons that they replaced. But the fifth valence electron remains free, having
no bonding responsibilities. When phosphorus atoms are substituted for silicon in a
crystal, many free electrons become available.

The most common method of doping is to coat a layer of silicon material with
phosphorus and then heat the surface. This allows the phosphorus atoms to diffuse into
the silicon. The temperature is then reduced so the rate of diffusion drops to zero. Other
methods of introducing phosphorus into silicon include gaseous diffusion, a liquid dopant
spray-on process, and a technique where phosphorus ions are precisely driven into the
surface of the silicon.

200 Photovoltaics

r::.^Pfp<

Boron
atom

Normal
bond v

Fig. 3. Boron substituted p-type silicon

The n-type silicon doped with phosphorus cannot form an electric field by itself. One also
needs p-type silicon. Boron, which has only three valence electrons, is used for doping p-
type silicon (Figure 3). Boron is introduced during silicon processing when the silicon is
purified for use in photovoltaic devices. When a boron atom takes a position in the crystal
lattice formerly occupied by a silicon atom, a bond will be missing an electron. In other
words, there is an extra positively charged hole.
3.4. Absorption and Conduction

In a photovoltaic cell, photons are absorbed in the p-layer. And it's very important to
"tune" this layer to the properties of incoming photons to absorb as many as possible, and
thus, to free up as many electrons as possible. Another challenge is to keep the electrons
from meeting up with holes and recombining with them before they can escape from the
photovoltaic cell. To do all this, we design the material to free the electrons as close to
the junction as possible, so that the electric field can help send the free electrons through
the conduction layer (the n-layer) and out into the electrical circuit (Figure 4). By
optimizing all these characteristics, one improves the photovoltaic cell's conversion
efficiency, which is how much of the light energy is converted into electrical energy by
the cell.

An Introduction to Energy Sources

201

MINIMIZE

MAXIMIZE

Reflection

V^1

n-layer

Junction

D-laver

Recombination
)

■S q- tJ 5-5 ^ 9

"□ i?23

■ + *■<•*■<■*{■**

ncnsp

sriSifi

^^^^^

Absorption

no
no

Conduction

■7T-

Fig. 4. Adsorption and conduction in the photovoltaic systems

3.5. Electrical contacts

Electrical contacts are essential to a photovoltaic cell because they bridge the connection
between the semiconductor material and the external electrical load, such as a light bulb.
The back contact of a cell, i.e., on the side away from the incoming sunlight i.e. is
relatively simple. It usually consists of a layer of aluminum or molybdenum metal. But
the front contact, on the side facing the sun, i.e. is more complicated. When sunlight is
shined on the photovoltaic cell, electron current flows all over its surface. If we attach
contacts only at the edges of the cell, it will not work well because of the great electrical
resistance of the top semiconductor layer. Only a small number of electrons would make
it to the contact.

To collect the maximum current, one must place contacts across the entire surface of a
photovoltaic cell. This is normally done with a "grid" of metal strips or "fingers."
However, placing a large grid, which is opaque, on the top of the cell shades active parts
of the cell from the sun. The cell's conversion efficiency is thus significantly reduced. To
improve the conversion efficiency, we must minimize these shading effects. Another
challenge in cell design is to minimize the electrical resistance losses when applying grid
contacts to the solar cell material. These losses are related to the solar cell material's
property of opposing the flow of an electric current, which results in heating the material.
Therefore, in designing grid contacts, we must balance shading effects against electrical
resistance losses. The usual approach is to design grids with many thin, conductive
fingers spreading to every part of the cell's surface. The fingers of the grid must be thick

202 Photovoltaics

enough to conduct well (with low resistance), but thin enough not to block much of the
incoming light. This kind of grid keeps resistance losses low while shading only about
3% to 5% of the cell's surface.

Grids can be expensive to make and can affect the cell's reliability. To make top-surface
grids, we can either deposit metallic vapors on a cell through a mask or paint them on via
a screen-printing method. Photolithography is the preferred method for the highest
quality, but has the greatest cost. This process involves transferring an image via
photography, as in modern printing. An alternative to metallic grid contacts is a
transparent conducting oxide (TCO) layer such as tin oxide (SnC>2). The advantage of
TCOs is that they are nearly invisible to incoming light, and they form a good bridge
from the semiconductor material to the external electrical circuit. TCOs are very useful in
manufacturing processes involving a glass superstate, which is the covering on the sun-
facing side of a PV module. Some thin-film PV cells, such as amorphous silicon and
cadmium telluride, use superstates. In this process, the TCO is generally deposited as a
thin film on the glass superstate before the semiconducting layers are deposited. The
semiconducting layers are then followed by a metallic contact that will actually be the
bottom of the cell. The cell is actually constructed "upside down," from the top to the
bottom. But the construction technique is not the only thing that determines whether a
metallic grid or TCO is best for a certain cell design. The sheet resistance of the
semiconductor is also an important consideration. In crystalline silicon, for example, the
semiconductor carries electrons well enough to reach a finger of the metallic grid.
Because the metal conducts electricity better than a TCO, shading losses are less than
losses associated with using a TCO. Amorphous silicon, on the other hand, conducts very
poorly in the horizontal direction. Therefore, it benefits from having a TCO over its entire
surface.

3.6. Antireflective coating

Since, silicon is a shiny gray material and can act as a mirror, reflecting more than 30%
of the light that shines on it. To improve the conversion efficiency of a solar cell, to
minimize the amount of light reflected so that the semiconductor material can capture as
much light as possible to use in freeing electrons. Two techniques are commonly used to

An Introduction to Energy Sources 203

reduce reflection. The first technique is to coat the top surface with a thin layer of silicon
monoxide (SiO). A single layer reduces surface reflection to about 10%, and a second
layer can lower the reflection to less than 4%. A second technique is to texture the top
surface. Chemical etching creates a pattern of cones and pyramids, which capture light
rays that might otherwise to deflect away from the cell. Reflected light is redirected down
into the cell, where it has another chance to be absorbed.
4. Photovoltaic module performance ratings

Generally, the performances rating of photovoltaic are expressed in terms of peak watt.
The peak watt (W p ) rating is determined by measuring the maximum power of a PV
module under laboratory conditions of relatively high light level, favorable air mass, and
low cell temperature. But these conditions are not typical in the real world. Therefore,
one may uses a different procedure, known as the NOCT (Normal Operating Cell
Temperature) rating. In this procedure, the module first equilibrates with a specified
ambient temperature so that maximum power is measured at a nominal operating cell
temperature. This NOCT rating results in a lower watt value than the peak-watt rating,
but it is probably more realistic. Neither of these methods is designed to indicate the
performance of a solar module under realistic operating conditions. Another technique,
the AMPM Standard, involves considering the whole day rather than "peak" sunshine
hours. This standard, which seeks to address the practical user's needs, is based on the
description of a standard solar global-average day (or a practical global average) in terms
of light levels, ambient temperature, and air mass. Solar arrays are designed to provide
specified amounts of electricity under certain conditions. The following factors are
usually considered when determining array performance: characterization of solar cell
electrical performance, determination of degradation factors related to array design and
assembly, conversion of environmental considerations into solar cell operating
temperatures, and calculation of array power output capability.

4.1. Power output.

Power available at the power regulator, specified either as peak power or average power
produced during one day.

4.2. Energy output.

204 Photovoltaics

The energy is expressed as watt-hour or Wh. This indicates the amount of energy
produced during a certain period of time. The parameters are output per unit of array area
(Wh/m 2 ), output per unit of array mass (Wh/kg), and output per unit of array cost (Wh/$).
4.3. Conversion efficiency.
This parameter is defined as

Energy output from array
X 100

Energy input from sun
This last parameter is often given as a power efficiency, equal to "power output from
array" / "power input from sun" x 100%. Power is typically given in units of watts (W),
and energy is typical in units of watt-hours (Wh). To ensure the consistency and quality
of photovoltaic systems and increase consumer confidence in system performance,
various groups such as the Institute of Electrical and Electronics Engineers (IEEE) and
the American Society for Testing and Materials (ASTM) are working on standards and
performance criteria for photovoltaic systems.
5. Reliability of photovoltaic Systems

Reliability of photovoltaic arrays is an important factor in the cost of systems and in
consumers accepting this technology. The photovoltaic cell itself is considered a "solid-
state" device with no moving parts, and therefore, it is highly reliable and long-lived.
Therefore, reliability of photovoltaic usually focuses not on cells, but on modules and
systems. One way to measure reliability is the rate of failure of particular parts. The
failure of solar cells mostly involves cell cracking, interconnect failures (resulting in open
circuits or short circuits), and increased contact resistance. Module-level failures include
glass breakage, electrical insulation breakdown, and various types of encapsulate failures.

Fault-tolerant circuit design involves using various redundant features in the circuit to
control the effect of partial failure on overall module yield and array power degradation.
Degradation can be controlled by dividing the modules into a number of parallel solar
cell networks called branch circuits. This type of design can also improve module losses
due to broken cells and other circuit failures. Bypass diodes or other corrective measures
can mitigate the effects of local cell hot-spots. Replacement of the entire module is a final

An Introduction to Energy Sources 205

option in dealing with photovoltaic array failures. However, today's component failure
rates are low enough that, with multiple-cell interconnects, series/paralleling, and bypass
diodes; it is possible to achieve high levels of reliability.
6. Classification of photovoltaic systems

Photovoltaic power systems are generally classified according to their functional and
operational requirements, their component configurations, and how the equipment is
connected to other power sources and electrical loads. The two principle classifications
are grid-connected or utility-interactive systems and stand-alone systems. Photovoltaic
systems can be designed to provide DC and/or AC power service, can operate
interconnected with or independent of the utility grid, and can be connected with other
energy sources and energy storage systems.
6.1. Grid-Connected (Utility-Interactive) PV Systems

Grid-connected or utility-interactive photovoltaic systems are designed to operate in
parallel with and interconnected with the electric utility grid. The primary component in
grid-connected photovoltaic systems is the inverter, or power conditioning unit (PCU).
The PCU converts the DC power produced by the photovoltaic array into AC power
consistent with the voltage and power quality requirements of the utility grid, and
automatically stops supplying power to the grid when the utility grid is not energized
(Figure 5). A bi-directional interface is made between the photovoltaic system AC output
circuits and the electric utility network, typically at an on-site distribution panel or
service entrance. This allows the AC power produced by the photovoltaic system to either
supply on-site electrical loads, or to back feed the grid when the photovoltaic system
output is greater than the on-site load demand. At night and during other periods when
the electrical loads are greater than the photovoltaic system output, the balance of power
required by the loads is received from the electric utility This safety feature is required in
all grid-connected photovoltaic systems, and ensures that the photovoltaic system will not
continue to operate and feed back onto the utility grid when the grid is down for service
or repair.

206

Photovoltaics

AC loads

▲

PV Array

Inverter/Power Conditioner

Distribution
panel

Electric Utility

Fig. 5. Diagram of grid-connected photovoltaic system

6.2. Stand-Alone photovoltaic systems

Stand-alone photovoltaic systems are designed to operate independent of the electric
utility grid, and are generally designed and sized to supply certain DC and/or AC
electrical loads. These types of systems may be powered by a photovoltaic array only, or
may use wind, an engine-generator or utility power as an auxiliary power source in what
is called a photovoltaic -hybrid system. The simplest type of stand-alone photovoltaic
system is a direct-coupled system, where the DC output of a photovoltaic module or array
is directly connected to a DC load (Figure 6). Since there is no electrical energy storage
(batteries) in direct-coupled systems, the load only operates during sunlight hours,
making these designs suitable for common applications such as ventilation fans, water
pumps, and small circulation pumps for solar thermal water heating systems. Matching
the impedance of the electrical load to the maximum power output of the photovoltaic
array is a critical part of designing well-performing direct-coupled system. For certain
loads such as positive-displacement water pumps; a type of electronic DC-DC converter,
called a maximum power point tracker (MPPT) is used between the array and load to
help better utilize the available array maximum power output.

PV Array

DC Load

Fig. 6. Simplest type of stand-alone PV system

An Introduction to Energy Sources

207

In many stand-alone photovoltaic systems, batteries are used for energy storage. Figure 7
shows a diagram of a typical stand-alone PV system powering DC and AC loads. Figure
8 shows how a typical photovoltaic hybrid system might be configured.

Charge
Controller

PV Array

DC Load

Battery

Inverter

AC Load

Fig. 7. Diagram of stand-alone PV system with battery storage powering DC and AC
loads

PV Array

Rectifier

Engine-generator,
wind turbine or grid backup

Charge

Controller

Battery

DC Load

Inverter

AC load

Fig. 8. Diagram of photovoltaic hybrid system

7. Non-silicon based photovoltaic systems

The alternative material and technology used in manufacturing photovoltaic components,
termed as second and third generation photovoltaic technologies include less-costly raw
material and manufacturing techniques. Second generation photovoltaic imply thin-film
solar cells, that use amorphous silicon or other compounds with semi-conducting
properties, which are deposited on flexible substrates ranging from glass to plastics and
other polymers. Third generation technologies include Organic, Nano and Spheral

208 Photovoltaics

technologies. Most of these are presently in the process of development and are soon
expected to be commercially produced

7.1. Thin film technology

Thin- film silicon solar cells offset many of the disadvantages of the conventional silicon
cells by using a fraction of the pure silicon required in manufacturing solar cells. They
are also easier to manufacture and easy to use in a variety of applications.
Thin film solar cells are made by depositing a thin layer of semiconductor on a
supporting material (substrates) such as glass, stainless steel or polyimide through a
process called Chemical Vapor deposition. The materials selected for deposition are
strong light absorbers, most commonly amorphous silicon (a-Si), cadmium telluride
(CdTe) and copper indium (gallium) diselenide (CIS or CIGS). These materials are
suitable for deposition over large substrate areas (up to 1 meter) and hence allow high
volume manufacturing. In terms of costs, amorphous silicon thin film solar cells use less
than 1% of the silicon used in conventional cells, and the material costs are also lower for
cells using CdTe or CIS technologies. These cells also do not require assembling and are
flexible, hence having versatile applications. The efficiency levels of these cells range
between 6 to 8 %. The market share for thin-film technology based solar cells ranged
between 7 and 8 % in 2002

7.2. Amorphous Silicon (a-Si)

Used mostly in consumer electronic products, which require lower power output and cost
of production, amorphous silicon has been the dominant thin-film PV material since it
was first discovered in 1974. Amorphous silicon is a non-crystalline form of silicon i.e.
its silicon atoms are disordered in structure. A significant advantage of a-Si is its high
light absorptivity, about 40 times higher than that of single-crystal silicon. Therefore only
a thin layer of a-Si is sufficient for making PV cells (about 1 micrometer thick as
compared to 200 or more micrometers thick for crystalline silicon cells). Also, a- Si can
be deposited on various low-cost substrates, including steel, glass and plastic, and the
manufacturing process requires lower temperatures and thus less energy. So the total
material costs and manufacturing costs are lower per unit area as compared to those of
crystalline silicon cells.

An Introduction to Energy Sources 209

Despite the promising economic advantages, a-Si still has two major roadblocks to
overcome. One is the low cell energy conversion efficiency, ranging between 59%, and
the other is the outdoor reliability problem in which the efficiency degrades within a few
months of exposure to sunlight, losing about 10 to 15%. The average price for a a-Si
module cost about $7 per watt in 1995.

7.3. Cadmium Telluride (CdTe)

As a polycrystalline semiconductor compound made of cadmium and tellurium, CdTe has
a high light absorptivity level, only about a micrometer thick can absorb 90% of the solar
spectrum. Another advantage is that it is relatively easy and cheap to manufacture by
processes such as high-rate evaporation, spraying or screen printing. The conversion
efficiency for a CdTe commercial module is about 7%, similar to that of a-Si. The
instability of cell and module performance is one of the major drawbacks of using CdTe
for PV cells. Another disadvantage is that cadmium is a toxic substance. Although very
little cadmium is used in CdTe modules, extra precautions have to be taken in
manufacturing process.

7.4. Copper Indium Diselenide (CuInSe2, or CIS)

A polycrystalline semiconductor compound of copper, indium and selenium, CIS has
been one of the major research areas in the thin film industry. The reason for it to receive
so much attention is that CIS has the highest "research" energy conversion efficiency of
17.7% in 1996 is not only the best among all the existing thin film materials, but also
came close to the 18% research efficiency of the polycrystalline silicon PV cells. (A
prototype CIS power module has a conversion efficiency of 10 %.) Being able to deliver
such high energy conversion efficiency without suffering from the outdoor degradation
problem, CIS has demonstrated that thin film PV cells are a viable and competitive
choice for the solar industry in the future.

CIS is also one of the most light-absorbent semiconductors; 0.5 micrometers can absorb
90% of the solar spectrum. CIS is an efficient but complex material. Its complexity
makes it difficult to manufacture. Also, safety issues might be another concern in the
manufacturing process as it involves hydrogen selenide, an extremely toxic gas. So far,
CIS is not commercially available yet although Siemens Solar has plans to commercialize
CIS thin-film PV modules.

210 Photovoltaics

7.5. Nanotechnology in photovoltaic

Various nanosize materials are under investigation; the major advantage of nanoparticle
in the field of photovoltaics is increases in the charge transfer rate and tunability, which
can be achieved by reducing the particle size. By controlling the particle size one can
tune the band gap of the material so that it matches well with the solar spectrum and
render the nanoparticles ideal for photovoltaic applications. Various attempts have been
under investigation and it is believed that the appropriate photovoltaic system with
maximum efficiency will be achieved in sooner.

7.6. Organic technology

Organic solar cells are based on the photosynthesis process in plants. The absorption of
light in organic cells is done by the 'dye' which substitutes for the silicon in conventional
cells. This light causes the dye molecules to excite and release electrons that are
converted to electrical energy. The use of chemicals called dyes for the conversion
process has led to organic cells also being known as "dye-sensitized solar cells". The
absorption of light occurs in dye molecules that are in a highly porous film of Titanium
dioxide (Ti0 2 ). This causes the electron to be injected into Ti0 2 and is conducted to the

transparent conductive oxide layer. The material and manufacturing costs of these cells
are relatively much lower than conventional silicon photovoltaic cells. However, the low
efficiency rates (3 - 5 %) result in an overall increase in the costs. This technology is
presently being developed and expected to be produced commercially.
References

1. http://www. azom.com/details. asp?ArticleID=l 156#_From_Cells_to

2. http://www.fsec.ucf.edU/pvt/pvbasics/index.htm#HistofPV

3. http://wwwl .eere.energy.gov/solar/photoelectric_effect.html

4. http://www.infinitepower.org/pdf/FactSheet-l 1 .pdf

Chapter - 12

PHOTO ELECTROCHEMICAL CELLS

S. Navaladian

The importance of the energy sector is understood by human beings as the inventions of
so many instruments, weapons, equipment according to the requirements for well being.
The energy sources like petroleum products, coal, nuclear plants are one way or other are
used effectively by mankind. Since these sources are conventional sources, they can not
be long lasting sources as long as mankind exists. As far as the prediction about the
availability fossil fuels, they can available only up to 50 more years - the world
population increase drastically. As a result the mankind is in the critical situation of
looking for the alternative fuels. Lot of efforts has been put on the research on the energy
sector, particularly the alternative energy source development. Even before a century ago,
the efforts on harnessing the sunlight by the scientists in the various countries. The
sunlight is an open energy source for all except to the polar regions of earth where sun is
seen rarely. By using the photo-active materials trapping the light energy from the
sunlight and converting on to fuel or electric power is possible. This has been with solid
interfaces of P-N junction. The potential difference created by P-N junction imparts the
current in circuit. Instead of solid interface if an electrolyte is interfaced between
photoactive material (semiconductor) anode and noble metal cathode in electrolyte
medium, the electricity will be generated. This is known as photo electrochemical cells.
The electrochemical reaction takes place between the electrodes and electrolytes
particularly, oxidation at photo anode and reduction at noble metal cathode.
Electrochemical cells

The cell which contains an anode and cathode in an electrolyte giving or withdrawing
electrical energy with chemical reaction at the interface of electrolyte and electrode is
called an electrochemical cell. If electrical power is withdrawn from the cell, it is called
as Galvanic cell or voltaic cells. If the power is given to the cell, it is electrolytic cell.
Voltaic cell or galvanic cells

212

Photo electrochemical Cells

In this of cells, the chemical energy is converted to electrical energy. This Zinc more
readily loses electrons than copper, so placing zinc and copper metal in solutions of their
salts can cause electrons to flow through an external wire which leads from the zinc to the
copper.

eletrons

ZnSQ, CuS0 4

Fig.l. Sketch of a typical Galvanic cell

As a zinc atom provides the electrons, it becomes a positive ion and goes into aqueous
solution, decreasing the mass of the zinc electrode. On the copper side, the two electrons
received allow it to convert a copper ion from solution into an uncharged copper atom
which deposits on the copper electrode, increasing its mass. The two reactions are
typically written

Zn(s)->Zn 2+ (aq) + 2e"

Cu 2+ (aq) + 2e" -> Cu(s)
The letters in parentheses denote that Zinc goes from a solid state (s) into an aqueous
solution (aq) and vice versa for copper. The two reactions represented are called the half
cell reactions. This cell is called Daniel cell.

In order for the voltaic cell to continue to produce an external electric current, there must
be a movement of the sulfate ions in solution from the right to the left to balance the
electron flow in the external circuit. The metal ions themselves must be prevented from
moving between the electrodes, so some kind of porous membrane or other mechanism

An Introduction to Energy Sources 213

must provide for the selective movement of the negative ions in the electrolyte from the
right to the left.

Energy is required to force the electrons to move from the zinc to the copper electrode,
and the amount of energy per unit charge available from the voltaic cell is called the
electromotive force (emf) of the cell. Energy per unit charge is expressed in volts (1 volt
= 1 joule/coulomb).

Clearly, to get energy from the cell, one must get more energy released from the
oxidation of the zinc than it takes to reduce the copper. The cell can yield a finite amount
of energy from this process, the process being limited by the amount of material available
either in the electrolyte or in the metal electrodes. For example, if there were one mole of
the sulfate ions SO4 2 " on the copper side, then the process is limited to transferring two
moles of electrons through the external circuit. The amount of electric charge contained
in a mole of electrons is called the Faraday constant, and is equal to Avogadro's number
times the electron charge:
Faraday constant = F = N A e = 6.022 x 10 23 x 1.602 x 10" 19 = 96,485 Coulombs / mole
The energy yield from a voltaic cell is given by the cell voltage times the number of
moles of electrons transferred times the Faraday constant.
Electrical energy output = nFE ce n

The cell emf E ce n may be predicted from the standard electrode potentials for the two
metals. For the zinc/copper cell under the standard conditions, the calculated cell
potential is 1.1 volts. This positive cell potential shows that cell is spontaneous.
Electrolytic cells

Water electrolysis cell is coming under electrolytic cells and here the electric power is
given to the cell and H2 and O2 gases are released at the cathode and anode respectively.
The electroplating also comes under this category. In these reactions the electrical energy
is converted to chemical energy. Fig. 2 . shows the schematic representation of the
electrolytic cell for water electrolysis.

During the early history of the earth, hydrogen and oxygen gasses spontaneously reacted
to form the water in the oceans, lakes, and rivers we have today. That spontaneous
direction of reaction can be used to create water and electricity in a galvanic cell (as it
does on the space shuttle). However, by using an electrolytic cell composed of water, two

214

Photo electrochemical Cells

electrodes and an external source emf one can reverse the direction of the process and
create hydrogen and oxygen from water and electricity. The reaction at the anode is the
oxidation of water to O2 and acid while the cathode reduces water into H2 and hydroxide
ion. That reaction has a potential of -2.06 V at standard conditions. However, this process
is usually performed with [H + ] = 10" 7 M and [OH"] = 10" 7 M, the concentrations of
hydronium and hydroxide ions in pure water. Applying the Nernst Equation to calculate
the potentials of each half-reaction, we find that the potential for the electrolysis of pure
water is -1.23 V. To make the electrolysis of water to occur, one must apply an external
potential (usually from a battery of some sort) of greater than or equal to 1.23 V. In
practice, however, it is necessary to use a slightly larger voltage to get the electrolysis to
occur on a reasonable time scale. Pure water is impractical to use in this process because
it is an electrical insulator. That problem is circumvented by the addition of a minor
amount of soluble salts that turn the water into a good conductor. Such salts have subtle
effects on the electrolytic potential of water due to their ability to change the pH of water.
Such effects from the salts are generally so small that they are usually ignored.

Hydrogen gas

Oxygen gas

3 bubbles

Anode

-O

~0z

Water
Soluble
salt

_•

H 2 bubbles

cathode

Fig.2. Setup for the electrolysis of Water

An Introduction to Energy Sources 215

Photo electrochemical cells

This photo electrochemical cell is also coming under the voltaic cells. The difference
between these galvanic cells and photo electrochemical cell, in principle, is chemical
energy is converted into electrical energy in the former, whereas light energy is converted
in the electrical energy or chemical energy in the form of fuel (H2). The schematic
representation of photo electrochemical is shown in the Fig. 3. a and 3. b. The foundation
of modern photo electrochemistry, marking its change from a mere support of
photography to a thriving research direction on its own, was laid down by the work of
Brattain and Garret and subsequently Gerischer who undertook the first detailed
electrochemical and photo electrochemical studies of the semiconductor-electrolyte
interface. Research on photo electrochemical cells went through a frantic period after the
oil crisis in 1973, which stimulated a worldwide quest for alternative energy sources.
Within a few years well over a thousand publications appeared. Investigations focused on
Two types of cells whose principle of operation is shown in Fig. 3. The first type is the
regenerative cell, which converts light to electric power leaving no net chemical change
behind. Photons of energy exceeding that of the band gap generate electron-hole pairs,
which are separated by the electric field present in the space-charge layer. The negative
charge carriers move through the bulk of the semiconductor to the current collector and
the external circuit. The positive holes are driven to the surface where they are scavenged
by the reduced form of the redox relay molecule (R), oxidizing it:

h + + R -> O.
The oxidized form O is reduced back to R by the electrons that re-enter the cell from the
external circuit. Much of the work on regenerative cells has focused on electron-doped
(n-type) II/VI or III/V semiconductors using electrolytes based on sulphide/polysulphide,
vanadium (II) /vanadium (III) or I2/I redox couples. Conversion efficiencies of up to
19.6% have been reported for multijunction regenerative cells. The second type,
photosynthetic cells, operate on a similar principle except that there are two redox
systems: one reacting with the holes at the surface of the semiconductor electrode and the
second reacting with the electrons entering the counter-electrode. In the example shown,
water is oxidized to oxygen at the semiconductor photoanode and reduced to hydrogen at
the cathode.

216

Photo electrochemical Cells

(a) Semiconductor

elect rod

Counter-
electrode

■ e ^/ Conduction
band

(b) Semiconductor Counter-

electrode electrode

■ e _^ / Conduction

Fig. 3. Schematic representation of principle of operation of photo electrochemical cells
based on n-type semiconductors, a, Regenerative-type cell producing electric current
from sunlight; b, a cell that generates a chemical fuel, hydrogen, through the photo-
cleavage of water.

The overall reaction is the cleavage of water by sunlight. Titanium dioxide has been the
favoured semiconductor for these studies, following its use by Fujishima and Honda for
water photolysis. Unfortunately, because of its large band gap (3-3.2 eV), as shown in
Fig. 4), TiC>2 absorbs only the ultraviolet part of the solar emission and so has low
conversion efficiencies. Numerous attempts to shift the spectral response of TiC>2 into the
visible, or to develop alternative oxides affording water cleavage by visible light, have so
far failed. In view of these prolonged efforts, disillusionment has grown about the
prospects of photo electrochemical cells being able to give rise to competitive
photovoltaic devices, as those semiconductors with band gaps narrow enough for
efficient absorption of visible light are unstable against photo corrosion. The width of the
band gap is a measure of the chemical bond strength. Semiconductors stable under
illumination, typically oxides of metals such as titanium or niobium, therefore have a
wide band gap, an absorption edge towards the ultraviolet and consequently insensitivity
to the visible spectrum. The resolution of this dilemma came in the separation of the
optical absorption and charge-generating functions, using an electron

An Introduction to Energy Sources

217

Transfer sensitizer absorbing in the visible to inject charge carriers across the
semiconductor-electrolyte junction into a substrate with a wide band gap, and therefore
stable. Fig. 3. a and 3.b shows the operational principle of such a device.

vacuum

- E i

i NHE

(3.0 eV)

-3

- -1.5

_ (2.25 eV) (3.2 eV) ^

-3.5

- -0.1

f < 2 - 25eV > / (3.2 eV)

4.0

- -0.5

GaAs

C ^ ZnC (2.6 eV) Ti0 2

"_ Eu 2+,3+

4.5

- 0.0

(1.4

■

-- H 2 0/H 2

5.0

- 0.5

eV)

_- [Fe(CN) 6 ] 3 "' 4

■

- Fe 2+ /Fe 3+

5.5

- 1.0

_ H 2 0/0 2

6.0

- 1.5

-- Ce 4+,3+

CdSe

6.5

- 2.0

(1.7eV)

7.0

- 2.5

7.5

- 3.0

Fe,0 3

(2.1 eV)

8.0

-3.5

o 2

(3.8

eV)

Fig. 4. Band positions of several semiconductors in contact with aqueous electrolyte at pH
1.

The lower edge of the conduction band and upper edge of the valence band are presented
along with the band gap in electron volts. The energy scale is indicated in electron volts
using either the normal hydrogen electrode (NHE) or the vacuum level as a reference.
Note that the ordinate presents internal and not free energy. The free energy change of an
electron-hole pair is smaller than the band gap energy due to the translational entropy of
the electrons and holes in the conduction and valence band, respectively. On the right
side the standard potentials of several redox couples are presented against the standard
hydrogen electrode potential.
Nanocrystalline junctions and interpenetrating networks

The need for dye-sensitized solar cells to absorb far more of the incident light was the
driving force for the development of mesoscopic semiconductor materials — minutely

218 Photo electrochemical Cells

structured materials with an enormous internal surface area — which have attracted great
attention during recent years. Mesoporous oxide films are made up of arrays of tiny
crystals measuring a few nanometers across. Oxides such as HO2, ZnO, SnCh and M>205,
or chalcogenides such as CdSe, are the preferred compounds. These are interconnected to
allow electronic conduction to take place. Between the particles are mesoscopic pores
filled with a semi conducting or a conducting medium, such as a p-type semiconductor, a
polymer, a hole transmitter or an electrolyte. The net result is a junction of extremely
large contact area between two interpenetrating, individually continuous networks.
Particularly intriguing thing is the ease with which charge carriers percolate across the
mesoscopic particle network, making the huge internal surface area electronically
addressable. Charge transport in such mesoporous systems is under intense investigation
today and is best described by a random walk model. The semiconductor structure,
typically 10 mm thick and with a porosity of 50%, has a surface area available for dye
chemisorption over a thousand times that of a flat, unstructured electrode of the same
size. If the dye is chemisorbed as a monomolecular layer, enough can be retained on a
given area of electrode to provide absorption of essentially all the incident light. Fig. 5.
shows an electron micrograph of a nanocrystalline Ti0 2 film with a grain size in the
range of 10-80 nm. The nanostructure of the semiconductor introduces profound changes
in its photo electrochemical properties. Of great importance is the fact that a depletion
layer cannot be formed in the solid - the particles are simply too small. The voltage drop
within the nanocrystals remains small under reverse bias, typically a few mV. As a
consequence there is no significant local electric field present to assist in the separation of
photogenerated electron-hole pairs. The photo response of the electrode is determined by
the rate of reaction of the positive and negative charge carriers with the redox couple
present in the electrolyte. If the transfer of electrons to the electrolyte is faster than that of
holes, then a cathodic photocurrent will flow, like in a p-type semiconductor/liquid
junction. In contrast, if hole transfer to the electrolyte is faster, then anodic photocurrent
will flow, as in n-type semiconductor photo electrochemical cells.

Striking confirmation of the importance of these kinetic effects came with the
demonstration that the same nanocrystalline film could show alternatively n- or p-type
behavior, depending on the nature of the hole or electron scavenger present in the

An Introduction to Energy Sources 219

electrolyte phase. This came as a great surprise to a field where the traditional thinking
was to link the photo response to formation of a charge-depletion layer at the
semiconductor-electrolyte interface.

Fig. 5. Scanning electron micrograph of the surface of a mesoporous anatase film
prepared from a hydro thermally processed Ti02 colloid. The exposed surface planes
have mainly {101} orientation.

What, then, is the true origin of the photo voltage in dye-sensitized solar cells? In the
conventional picture, the photo voltage of photo electrochemical cells does not exceed
the potential drop in the space-charge layer but nanocrystalline cells can develop photo
voltages close to 1 V even though the junction potential is in the mV range. It has been
suggested that a built-in potential difference at the back contact of the nanocrystalline
film with the conducting glass is responsible for the observed photo voltage. Other
evidence suggests that under illumination, electron injection from the sensitizer increases
the electron concentration in the nanocrystalline electrode, raising the Fermi level of the
oxide and thus shifting its potential. From recent electrical impedance studies, it seems
that both changes — the potential drop across the back contact and the Fermi level shift
of the TiC>2 nanoparticles — contribute to the photo voltage of dye-sensitized solar cells.
Accumulations layers can be produced in the nanocrystals under forward bias when
majority carriers are injected, rendering the film highly conductive. Under reverse bias
the carriers are withdrawn, turning it into an insulator. Thus, by changing the applied

220

Photo electrochemical Cells

potential, the film can be switched back and forth from a conducting to an insulating
state. Space-charge limitation of the current (arising from limitation of the density of
charge carriers because they are repelled by each other's electric field) is not observed as
the injected majority carriers are efficiently screened by the electrolyte present in the
pores surrounding the nanoparticles.

The factors controlling the rate of charge carrier percolation across the nanocrystalline
film are under intense scrutiny. A technique known as intensity-modulated impedance
spectroscopy has proved to be an elegant and powerful tool, for addressing these and
other important questions related to the characteristic time constants for charge carrier
transport and reaction dynamics. An interesting feature specific to nanocrystalline
electrodes is the appearance of quantum confinement effects. These appear when the
films are made up of small quantum dots, such as 8-nm-sized CdTe particles. Such layers
have a larger band gap than the bulk material, the band edge position being shifted with
respect to the positions indicated in Figure. 4 for macroscopic materials.
The conduction band redox potential is lowered and that of the valence band is increased.
As a consequence, electrons and holes can perform reduction and oxidation reactions that
cannot proceed on bulk semiconductors. The astounding photo electrochemical
performance of nanocrystalline semiconductor junctions is illustrated in Fig. 7. Where
the comparison the photo response of an electrode made of single-crystal anatase, one of
the crystal forms of TiC>2, with that of a mesoporous TiC>2 film.

Both electrodes are sensitized by the ruthenium complex cz's-RuL2(SCN)2 (L is 2,2'-
bipyridyl-4-4'-dicarboxylate), which is adsorbed as a monomolecular film on the titania
surface.

Conducting
glass \

TiO

-0.5

0.5

1.0

Maximum
volt »ge

Red^f7° X
-Mediator

Interception "*

"' Diffusion

- s°/s+

Cathode

Fig. 6. Schematic of operation of the dye-sensitized electrochemical photovoltaic cell.

An Introduction to Energy Sources

221

The incident-photon-to-current conversion efficiency (IPCE) is plotted as a function of
wavelength. The photo anode, made of a mesoporous dye-sensitized semiconductor,
receives electrons from the photo-excited dye which is thereby oxidized, and which in
turn oxidizes the mediator, a redox species dissolved in the electrolyte. The mediator is
regenerated by reduction at the cathode by the electrons circulated through the external
circuit The IPCE value obtained with the single-crystal electrode is only 0.13% near 530
nm, where the sensitizer has an absorption maximum, whereas it reaches 88% with the
nanocrystalline electrode — more than 600 times as great. The photocurrent in standard
sunlight augments 10 3 — 10 4 times when passing from a single crystal to a nanocrystalline
electrode (standard, or full, sunlight is defined as having a global intensity (is) of 1,000
W m 2 , air mass 1.5; air mass is the path length of the solar light relative to a vertical
position of the Sun above the terrestrial absorber). This striking improvement is due
largely to the far better light harvesting of the dye-sensitized nanocrystalline film as
compared with a flat single-crystal electrode, but is also due, at least in part, to the
mesoscopic film texture favoring photo generation and collection of charge carriers.

a 0.15

~ 0.10
HI

— 0.05

iii

300

400 500 600 700 8

Wavelength (nm)

100

80 -

60 "

300 400 500 600 700

Wavelength ( nm )

800

Fig. 7. The nanocrystalline effect in dye-sensitized solar cells. In both cases, Ti02
electrodes are sensitized by the surface-anchored ruthenium complex cis-RuL2(SCN)2.
The incident-photon-to-current conversion efficiency is plotted as a function of the
excitation wavelength, a, Single-crystal anatase cut in the (101) plane, b, Nanocrystalline
anatase film. The electrolyte consisted of a solution of 0.3M Lil and 0.03M 12 in
acetonitrile

222 Photo electrochemical Cells

The overall conversion efficiency of the dye-sensitized cell is determined by the
photocurrent density measured at short circuit (z'ph), the open-circuit photo-voltage (Voc),
the fill factor of the cell (ff) and the intensity of the incident light (Is) hglobal4z'phVoc
(ff/Js) Under full sunlight, short-circuit photocurrents ranging from 16 to 22 mA cm-2
are reached with state-of-the-art ruthenium sensitizers, while Voc is 0.7-0.8 V and the fill
factor values are 0.65-0.75. A certified overall power conversion efficiency of 10.4% has
been attained at the US National Renewable Energy Laboratory30. Although this
efficiency makes dye-sensitized cells fully competitive with the better amorphous silicon
devices, an even more significant parameter is the dye lifetime achieved under working
conditions. For credible system performance, a dye molecule must sustain at least 108
redox cycles of photo-excitation, electron injection and regeneration, to give a device
service life of 20 years. The use of solvents such as valeronitrile, or y-butyro lactone,
appropriately purified, in the electrolyte formulation provides a system able to pass the
standard stability qualification tests for outdoor applications, including thermal stress for
1,000 h at 85 °C, and this has been verified independently.

Tandem cells for water cleavage by visible light

The advent of nanocrystalline semiconductor systems has rekindled interest in tandem
cells for water cleavage by visible light, which remains a highly prized goal of photo
electrochemical research. The 'brute force' approach to this goal is to use a set of four
silicon photovoltaic cells connected in series to generate electricity that is subsequently
passed into a commercial-type water electrolyzer. Solar-to-chemical conversion
efficiencies obtained are about 7%. Much higher efficiencies in the range of 12-20%
have been reported for tandem cells based on III/V semiconductors, but these single-
crystal materials cost too much for large-scale terrestrial applications. A low-cost tandem
device that achieves direct cleavage of water into hydrogen and oxygen by visible light
was developed recently. This is based on two photosystems connected in series as shown
in the electron flow diagram of Fig. 8. A thin film of nanocrystalline tungsten trioxide,
WO3 , or Fe2C>3 serves as the top electrode absorbing the blue part of the solar spectrum.
The valence band holes (h + ) created by band-gap excitation of the film oxidize water to
oxygen and the conduction-band electrons are fed into the second photosystem

An Introduction to Energy Sources

223

consisting of the dye-sensitized nanocrystalline TiC^ cell discussed above. The latter is
placed directly under the WO3 film, capturing the green and red part of the solar spectrum
that is transmitted through the top electrode. The photo voltage generated by the second
photosystem enables hydrogen to be generated by the conduction-band electrons.

4h + + H 2 0^0 2 + 4H +

4H + +4e^ 2H 2
The overall reaction corresponds to the splitting of water by visible light. There is close
analogy to the 'Z-scheme' (named for the shape of the flow diagram) that operates in
photosynthesis. In green plants, there are also two photosystems connected in series, one
that oxidizes water to oxygen and the other generating the compound NADPH used in
fixation of carbon dioxide. As discussed above, the advantage of the tandem approach is
that higher efficiencies can be reached than with single junction cells if the two
photosystems absorb complementary parts of the solar spectrum. At present, the overall
conversion efficiency from standard solar light to chemical energy achieved with this
device stands at 4.5%, and further improvements are underway.

-0.1

E°(H 2 /H 2

\'^

C -

l.6eV

> u

111

> 1.0

I — I

CB ofW0 3 *S.

- -

# # # I

Redox poten

E°(H 2 /H
2.

6eV

Dye sensitized
Ti0 2

# * #

\S H 2 Q

CB ofWC

Fig. 8. The Z-scheme of photocatalytic water decomposition by a tandem cell

224 Photo electrochemical Cells

Dye-sensitized solid heteroj unctions and ETA cells

Interest is growing in devices in which both the electron- and hole-carrying materials are
solids, but are grown as interpenetrating networks forming a heterojunction of large
contact area. From conventional wisdom one would have predicted that solar cells of this
kind would work very poorly, if at all. The disordered character of the junction and the
presence of the huge interface are features one tries to avoid in conventional photovoltaic
cells, because the disruption of the crystal symmetry at the surface produces electronic
states in the band gap of the semiconductor, enhancing the recombination of photo
generated carriers. The fact that molecular photovoltaic cells based on the sensitization of
nanocrystalline TiC>2 were able to achieve overall conversion efficiencies from solar to
electric power of over 10% encouraged work on solid-state analogues, that is, dye-
sensitized heterojunctions. The first devices of this type used inorganic p-type
semiconductors, for example Cul or CuSCN, as hole conductors replacing the redox
electrolyte. Respectable conversion efficiencies exceeding 1% have been reached with
such cells. But the lack of photostability of the Cu(I) compounds and the difficulty of
realizing a good contact between the two mesoscopic inorganic materials still present
considerable practical challenges. Organic charge-transport materials have advantages in
this respect. An amorphous hole conductor can be introduced into the mesoporous TiC>2
film by a simple spin-coating process and readily adapts its form to the highly corrugated
oxide surface. Cells based on a spirobisfluorene-connected arylamine hole transmitter38,
which fills the pores of a dye-sensitized nanocrystalline TiC>2 film, have reached a
conversion efficiency of 2.56% at full sunlight39. The high open-circuit voltage of these
devices, exceeding 900 mV, is particularly noteworthy and promising for further
substantial improvements in performance. In general, dye-sensitized heterojunction cells
offer great flexibility because the light absorber and charge-transport material can be
selected independently to obtain optimal solar energy harvesting and high photovoltaic
output. The great advantage of such a configuration is that the charge carriers are
generated by the dye precisely at the site of the junction where the electric field is
greatest, enhancing charge separation.

Extremely thin absorber (ETA) solar cells are conceptually close to dye-sensitized
heterojunctions. The molecular dye is replaced by an extremely thin (2-3 nm) layer of a

An Introduction to Energy Sources 225

small-band-gap semiconductor, such as CuInS2. A hole conductor such as CuSCN is
placed on top of the absorber, producing a junction of the PIN type (p-type
semiconductor/insulator/n-type semiconductor). The structure has the advantage of
enhanced light harvesting due to the surface enlargement and multiple scattering.
Because photo-induced charge separation occurs on a length scale of a few nanometres,
higher levels of defects and impurities can be tolerated than in flat thin-film devices,
where the minority carriers are required to diffuse several microns. On the other hand,
making PIN-junctions of such high contact area is difficult and this has hampered the
performance of these cells. Their conversion efficiency so far has remained below 5%,
which is less than one-third of the yield obtained with similar semiconductor materials in
a flat junction configuration. Organic materials have the advantage of being cheap and
easy to process. They can be deposited on flexible substrates, bending where their
inorganic competitors would crack. The choice of materials is practically unlimited, and
specific parts of the solar spectrum can be selectively absorbed. Although organic cells
are still considerably less efficient than single-crystal gallium arsenide or silicon,
progress has been impressive over the past few years. In particular, solar cells based on
interpenetrating polymer networks, polymer/fullerene blends, halogen-doped organic
crystals and the solid-state dye- sensitized devices mentioned above have shown
surprisingly high solar conversion efficiencies, currently reaching values of 2-3%.
Conducting polymers, for example poly-(phenylenevinylene) (PPV) derivatives or C60
particles, are attracting great interest as photovoltaic material. Bulk donor-acceptor
heterojunctions are formed simply by blending the two organic materials serving as
electron donor (p-type conductor) and electron acceptor (n-type conductor). The
advantage of these new structures over the flat-junction organic solar cells investigated
earlier is the interpenetration of the two materials that conduct positive and negative
charge carriers, reducing the size of the individual phase domains to the nanometre range.
This overcomes one of the problems of the first generation of organic photovoltaic cells:
the unfavourable ratio of exciton diffusion length to optical absorption length. An exciton
is a bound electron-hole pair produced by absorption of light; to be useful, this pair must
reach the junction and there dissociate into two free charge carriers — but excitons
typically diffuse only a few nanometres before recombining. Light is absorbed (and

226 Photo electrochemical Cells

generates excitons) throughout the composite material. But in the composite, the distance
the exciton has to travel before reaching the interface is at most a few nanometres, which
is commensurate with its diffusion length. Hence photo-induced charge separation can
occur very efficiently. Conversion efficiency from incident photons to current of over
50% has been achieved with a blend containing PPV and methanofullerene derivatives46.
The overall conversion efficiency from solar to electric power under full sunlight
achieved with this cell was 2.5%. Although these results are impressive, the performance
of the cell declined rapidly within hours of exposure to sunlight. In contrast, the output of
dye-sensitized solar cells is remarkably stable even under light soaking for more than
10,000 h. Similar long-term stability will be required for large-scale application of
polymer solar cells.
Summary

Photovoltaic devices based on interpenetrating mesoscopic networks have emerged as a
credible alternative to conventional solar cells. Common to all these cells is an ultrafast
initial charge separation step, occurring in femtoseconds, and a much slower back-
reaction.

This allows the charge carriers to be collected as electric current before recombination
takes place. Table 1 compares the performance of the new photo electrochemical systems
with conventional devices. Although still of lower efficiency, the nanostructured cells
offer several advantages over their competitors. They can be produced more cheaply and
at less of a cost in energy than silicon cells, for which 5 GJ have to be spent to make 1 m 2
of collector area. Unlike silicon, their efficiency increases with temperature, narrowing
the efficiency gap under normal operating conditions. They usually have a bifacial
configuration, allowing them to capture light from all angles. Transparent versions of
different colour can readily be made that could serve as electric power-producing
windows in buildings. These and other attractive features justify the present excitement
about these cells and should aid their entry into a tough market. Although significant
advances have been made, both in the basic understanding of photo electrochemical
devices and in the development of systems with good conversion efficiency and stability,
much additional research and development must be done before photo electrochemical
systems can be seriously considered for practical solar energy conversion schemes.

An Introduction to Energy Sources

227

Table 1. Performance of photovoltaic and photo electrochemical solar cells

Type of cell

Efficiency (%)

Research and
technology needs

Cell

Module

Crystalline silicon

10-15

Higher reduction yields,
lowering of cost and
energy content

Multicrystalline
silicon

9-12

Lower manufacturing
cost and
complexity

CuInSe 2

Replace indium (too
expensive and limited
supply), replace CdS
window layer, scale up
production

Dye-sensitized
nanostructured
materials

10-11

Improve efficiency and
high temperature
stability, scale up
production

Bipolar AlGaAs/Si
photo
electrochemical cells

19-20

Reduce materials cost,
scale up

Organic solar cells

2-3

Improve stability and
efficiency

^Efficiency defined as conversion efficiency from solar to electrical power.
References

1. http://atom.ecn.purdue.edu/~vurade/PEC%20Generation%20oP/o20Hvdrogen/

2. http://www.sciencemag.org/cgi/content/summary/301/5635/926

3. M. Gratzel, Nature, 2001(414) 338.

4. J. Kriiger, U. Bach, and M. Gratzel,. Appl. Phys. Lett. 2001 (79) 2085.

5. Halls, J. J. M., Pickler, K., Friend, R. H., Morati, S. C. and Holmes, A. B.. Nature
1995(376)498.

6. G.Yu, J., Gao, J. C.Hummelen, F. Wudi, and A. J Heeger,. Science 1995 ( 270)
1789.

7. D. Wohrle. D. Meissner. Adv. Mat. 1991 (130) 129.

Chapter - 13

HYDROGEN PRODUCTION
G. Magesh

Hydrogen: Fuel of the Future

Hydrogen is emerging as the favorite alternative to fossil fuels as an energy carrier.
Auto manufacturing, for example, have come up with models that run on either hydrogen
used as fuel in internal combustion engines (ICEs), or fuel cell cars that use gasoline in
the ICE and, additionally, a fuel cell producing electricity-using hydrogen as fuel.
Recently, a car running on just hydrogen completed a journey through continental
Australia — the grueling 4000 kilometer long journey proved that these cars are as tough
as any other. The US government has embarked on an initiative to develop technology
for the production, transportation and storage of hydrogen and using it as an alternative
fuel as and when the need arises. But there are plenty of technological challenges that
need to be addressed before hydrogen can become the day-to-day fuel.

1.5 -

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Fig.l. Relative emissions of carbon for various fuels and combustion engines

Fig.l. compares the relative carbon emissions per kilometer resulting from the use of
gasoline versus hydrogen in ICE alone as well as hybrid ICE + fuel cell vehicles. It is

An Introduction to Energy Sources 229

apparent that the use of fuel cell powered vehicles using hydrogen generated from
renewable energy sources brings down the emissions to almost zero.
The advantages of hydrogen as a universal energy medium are:

1. The combustion of hydrogen results in the formation of steam and liquid water. In this
respect, the use of hydrogen is completely safe from environmental standpoint.

2. It is non- toxic.

3. It is easily assimilated into the biosphere: its combustion products are recycled by
plants in the form of carbohydrates.

4. It is possible to produce hydrogen from the most abundant chemical on earth: water.
Hydrogen can be obtained electrolytically, photoelectrochemically, thermochemically, by
direct thermal decomposition or biochemically from water.

5. Hydrogen can be used as a feedstock for the chemical industry, enabling the
production of entire gamut of chemicals from hydrogen and conventional petrochemicals.

6. It is the most suitable fuel for use in fuel cells - direct conversion of chemical energy
into electricity without the heat route with an enhanced efficiency.

7. Transmission of energy in the form of hydrogen is more economical than through high
voltage AC lines for large distances.

Methods of producing hydrogen

Hydrogen is the most abundant element in the Universe. Hydrogen is the simplest of atoms,

composed of one proton and one electron. But pure, diatomic hydrogen (H 2 ) — the fuel of choice

for fuel cells — does not exist naturally. Since hydrogen easily combines with other elements,

one is most likely to find it chemically bound in water, biomass, or fossil fuels.

To get hydrogen into a useful form, it must be extracted from one of these sources. This process

requires energy. Accordingly, the cleanliness and renewability of this energy is of critical

importance. While a hydrogen - oxygen fuel cell operates without producing emissions,

producing hydrogen can give rise to significant greenhouse gases and other harmful byproducts.

Once obtained, hydrogen is a nearly ideal energy carrier. The various ways to obtain hydrogen

are :

Direct electrolysis

230 Hydrogen Production

Water electrolysis involves passing an electric current through water to separate it into hydrogen
(H 2 ) and oxygen (O2). Hydrogen gas rises from the negative cathode and oxygen gas collects at
the positive anode. The reactions involved in the electrolysis of water are:
Reduction electrode (Cathode):

2H 2 + 2e" ► 2 0H" + H 2

Oxidation electrode (Anode):

2 OH" ► H 2 + 1/2 2 + 2 e"

Complete cell reaction:

H 2 ► H 2 + 1/2 2

The values of the cathode and anode half-cell potentials, are known to be 0.401 V and -
0.828 V respectively at 25°C at a pH of 14. If the activities of water and the gaseous
species are considered unity, the cathode and anode potentials required according to
Nernst equation will be:

E c = -0.828 - 0.059 log a OH "
E a = 0.401 - 0.059 log a OH "

And the potential required to split water into H 2 and 2 ,i.e E a - E c is equal to 1.229 V.
Though the theoretical potential is 1.23 V for water electrolysis, in practice the actual
water decomposition will occur only above 1.7 V. The extra potential, which is essential
for the water decomposition, is called over potential. Overvoltage is evaluated mainly as
a function of current and temperature. Overvoltages are composed of activation or charge
transfer overvoltage, concentration or diffusion or mass transfer overvoltage and
resistance or ohmic over voltage. In general, an aqueous solution of caustic potash or
soda is used as the electrolyte for water electrolysis. The nature of anode and cathode is
decided based on their hydrogen and oxygen over voltages in the electrolytic medium in
addition to their stability in the particular medium. The cathode and anode are separated
by a diaphragm, which prevents the mixing of hydrogen and oxygen gases produced at
the cathode and anode surfaces respectively. The diaphragm should be stable in the
electrolyte and minimizes the diffusion of gas molecules without affecting the
conductivity of the medium.

Effect of temperature and pH on the decomposition potential

An Introduction to Energy Sources

231

The amount of electricity required to produce one mole of hydrogen by splitting one mole
of water is 2 Faradays, which is equal to 236.96 kJ of energy. Whereas, heat generated by
combustion of one mole of hydrogen is 285.58 kJ at 25 °C. The extra energy of 48.63 kJ
must be absorbed from the surrounding of electrolytic cell if the water is electrolyzed
with 1.229 V at 25 °C. Applying electrical energy of 285.58 kJ, i.e. 1.481 V, to a water
electrolyzer at 25 °C would generate hydrogen and oxygen isothermally. The values
1.229 and 1.481 V are called as the reversible and thermo-neutral voltage. The variation
of reversible and thermo-neutral voltage with temperature is shown in Fig. 2.

2.0

1.8-

1.6-

1.4

1.2

1.0-1

0.8

0.6

0.4-

0.2-

0.0

<f-*

"53
u
i—
<u
</)
>

H gas generated with evolution of heat

thermoneutral voltage

H 2 gas generated with absorption of heat

*"e\/e;-c/fj/ _

Not possible to generate H gas °'tege

100 200 300 400 500

Temperature(°C)

Fig. 2. Variation of cell potential as a function of temperature

It can be seen from the Fig. 2, that when the temperature increases the reversible voltage
decreases, whereas the thermo-neutral voltage slightly increases with temperature. It can
also be seen from Fig. 2 that, in the region below the reversible voltage, hydrogen
production is not possible. In the second region, the hydrogen is evolved with absorption
of heat from the surrounding. In the third region, the hydrogen is evolved with liberation
of heat, i.e. the extra energy as potential above the thermo-neutral potential is released as
heat energy. In general, the commercial industrial electrolytic cells are operating between
60-80 °C. The hydrogen and oxygen evolution potentials at various pH are shown in the
Fig. 3. It can been seen from the figure that the net potential needed for the hydrogen and
oxygen evolution at any given pH between to 14 is 1.229 V at 25 C.

232

Hydrogen Production

Potential (V)
1.229

Potential (V)

0.828

Fig. 3. Hydrogen and oxygen electrode potential against pH of the electrolyte

Due to the corrosive action on the electrode material especially at the anodes, the acidic
solutions are avoided for the water electrolysis. A typical water electrolysis cell is shown
in Fig. 4.

Electrolyte Solution

FigATypical water electrolysis cell

Electrolysis produces extremely pure hydrogen, which is necessary for some types of fuel cells.
But a significant amount of electricity is required to produce a usable amount of hydrogen from
electrolysis. In ideal case, this would come from renewable sources like wind and photo-catalysis.
But the hydrogen produced from electrolysis will in no way help reduce the pollution of
atmosphere if the electricity needed for the reaction is obtained through fossil fuels.

Steam-Methane Reformation

An Introduction to Energy Sources 233

Hydrogen can also be extracted or "reformed" from natural gas. A two-step process at
temperatures reaching 1100°C in the presence of a catalyst makes four parts hydrogen from one
part methane and two parts water. It is a relatively efficient and inexpensive process, and can be
made still more efficient with harvest of the waste heat (commonly referred to as cogeneration).
This latter feature makes steam-methane particularly attractive for local use.

Catalyst

CH 4 + H 2 — — — — ► CO + 3H 2
930°C

Catalyst

CO + H 2 — — — ►COs + H 2

350°C

While this process is well understood and can be implemented on a wide scale today, it produces
moderate emissions of carbon dioxide. Other innovative carbon-sequestration techniques are in
development. Unlike renewable electrolysis, steam-methane reformation depends on fluctuating
price of natural gas. Nonetheless, steam-methane reformation is poised to be the near-term
hydrogen production method of choice on the road towards completely renewable methods.
Biomass Gasification

Hydrogen can be extracted from hydrogen-rich biomass sources like wood chips and agricultural
waste. When heated in a controlled atmosphere, biomass converts to synthesis gas, which
primarily consists of carbon monoxide (CO), carbon dioxide (CO2), and hydrogen (H 2 ).
Gasification technology has been under intensive development over the last 2 decades. Large-
scale demonstration facilities have been tested and commercial units are in operation worldwide.
Fortunately, hurdles in biomass gasification have been economic rather than technical. Until
recently, biomass gasification has been employed to produce low-value products like electricity
or heat, which rarely justify the capital and operating costs. But the increasing demand for
hydrogen promises to make biomass gasification economically viable in the near future.

Hydrogen from Coal

Vast coal resources have often been viewed, as a potential source against future energy needs.
Unfortunately, coal mining pollutes and spoils the landscape, and burning coal produces many
harmful emissions. Yet coal does contain hydrogen, and techniques are being developed to
sequester the remaining carbon. These processes generally involve coal gasification to produce
hydrogen and electricity, followed by re-injection of CO2 or mineralization via carbonates.
Biochemical Hydrogen production

234 Hydrogen Production

Life requires metabolism, a complex web of redox chemistry. This requires energy, which can be
obtained by breaking of bonds (the multi-step breakdown of glucose to generate ATP and CO2) or
from electronic excitation. For example, plants, algae, cyanobacteria and photosynthetic bacteria
can use light energy to raise electrons into higher energy states. In case of plants, algae and
cyanobacteria, the source of excitable electrons is water. The excited electrons are stripped from
water, which then splits into oxygen and protons.

Hydrogen is produced in micro-organisms by enzymes capable of reducing free protons to
molecular hydrogen. Examples of these enzymes include hydrogenases and the nitrogenases.
The production of hydrogen by these enzymes is usually coupled to some other biochemical
processes. The energy used by these enzymes is usually in multiple steps from an organism's
central energy inputs and is provided in the form of electron carriers such as ferredoxin or
NADPH and energy yielding molecules like ATP. Obtaining useful amounts of hydrogen from
microorganisms will require increasing the efficiency of hydrogenases and overcoming other
obstacles. One problem is that some hydrogenases and nitrogenases are inhibited by oxygen.
Oxygen is produced by photo-system II (PSII) during oxygenic photosynthesis.
In the summer of 2001, researchers manipulated the photosynthetic process of spinach plants to
produce hydrogen. But these biological means of hydrogen production are known only as
laboratory experiments. Intense research persists to better understand ways to improve these
hydrogen production methods. Quantum leaps in this field could be the equivalent of striking oil.
Biological hydrogen production is the most challenging area of biotechnology with
respect to environmental problems. The future of biological hydrogen production
depends not only on research advances, i.e. improvement in efficiency through
genetically engineered microorganisms and/or the development of bioreactors, but also
on economic considerations (the cost of fossil fuels), social acceptance, and the
development of hydrogen energy systems.
Thermo-chemical decomposition of water:

The decomposition of water into hydrogen and oxygen can be achieved when energy is
supplied in the form of heat and work. The positive value of AG decreases with increase
in temperature, but rather slowly because of the nearly constant enthalpy change, as a
function of temperature and AG becomes zero around 4700K. This means that even the
highest temperature available from a nuclear reactor, in the range of 1300K, is not
sufficient to decompose water. Therefore, single-step thermal decomposition of water is
difficult unless other methods like electrolysis are resorted to. Two step decomposition

An Introduction to Energy Sources 235

of water wherein a metal oxide, metal hydride or hydrogen halide is involved according
to the equations:

H 2 + M ► MO + H 2

MO ► M + 0.5 2

H 2 + M ► MH 2 + 0.5 2

MH 2 ► M + H 2

H 2 + X 2 ► 2 HX + 0.5 2

2 HX ► H 2 + X 2

However, even these two-step routes require temperatures of the order of 1273 K or
more. Water cannot be decomposed in one or two thermo-chemical steps when the
available temperature is below 1273 K. However this can be done in a multiple-step
process wherein each step is easy to accomplish with either a negative or a little positive
AG for the reaction. For example if the desired reactions is

H 2 ► H 2 + 0.5 2 (1)

it can be achieved in a sequence of steps as follows:

2H 2 (g ) + I 2(g) + S0 2(g) ► 2HI(g) + H 2 S0 4 ( g ) (2)

H 2 S0 4(g) ► H 2 (g) + S0 2(g) + 0.5 02(g) (3)

Ni (s) + 2 HI (g) ► Nil 2(s) + H 2(g) (4)

Nil 2(s) ► Ni (s) + I 2(g) (5)

In this sequence the first reaction has a large positive AG (87.6 kJ/reaction) while all
other reactions have negative AG values. Replacing step (1) by the following step will
give a negative AG value.

2 H 2 0( g ) + I 2 ( g ) + S0 2 ( g ) ► 2 HI( aq ) + H 2 SO/t(aq) (6)

Carrying out the reaction in the four steps (Equations 6,3,4 and 5) at 300, 510, 570 and
1070K respectively requires -74.3 kJ. Therefore any thermochemical cycle can be
chosen by incorporating the following four reaction steps : water decomposition or
hydrolysis, hydrogen generation, oxygen generation, and the regeneration of any
intermediates formed. Some other therm-chemical cycles that are available for hydrogen
generation are

236 Hydrogen Production

Mark 15 process (iron-halogen system)
Mark 13 process (sulfur dioxide-iodine system)
Photochemical hydrogen production:

A photochemical hydrogen production is similar to a thermochemical system, in that it
also employs a system of chemical reactants, which carry out the splitting of water.
However, the driving force is not thermal energy but light, generally solar light. In this
sense, this system is similar to the photosynthetic system present in green plants. One can
effectively utilize photochemical means to promote endergonic (energy requiring)
reactions. The sensitized oxidation of water by Ce 4+ using irradiation of 254nm light by
the following reaction is known.

Ce 4+ +0.5H 2 O ► Ce 3+ + 0.25 2 + H + AH =3.8kcal/mol

Ce 3+ can be used with light of lower wavelength to promote the hydrogen generation
reaction:

Ce 3+ + H 2 ► Ce 4+ + 0.5 H 2 + OH"

The quantum efficiency of these processes is very low. Similarly Ru(bpy)3 2+ and related
complexes have relatively low excited-state lifetimes and can serve as electron donors or
electron acceptors. A typical reaction is:

[AR 2 ] 2+ (C10 4 ) 2 2 " — ^ ► *[AR 2 ] 2+ (C10 4 ) 2 2 -

excited state
<[AR 2 ] 2+ (C10 4 ) 2 2 - + H 2 ► H 2 + 0.5 2 + [AR 2 ] 2+ (C10 4 ) 2 2

where R = C18H35 andA= Ruthenium bipyridyl complex

Fig. 5. Ruthenium bipyridyl complex

An Introduction to Energy Sources

237

Photoelectrochemical hydrogen production:

In its simplest form, a photoelectrochemical (PEC) hydrogen production cell consists of a
semiconductor electrode and a metal counter electrode immersed in an aqueous
electrolyte. When light is incident on the semiconductor electrode, it absorbs part of the
light and generates electricity. This electricity is then used for the electrolysis of water.
Fujishima and Honda first demonstrated the electrolysis of water using solar energy in a
PEC cell about 30 years ago. A schematic of their cell is shown in the Fig. 6.

Fig. 6. Schematic showing the structure of a PEC cell

As seen from the diagram, the cell consists of a semiconductor (TiC>2) photo-anode,

which is irradiated with the UV-Visible radiation. The counter electrode is a metal.

Following processes take place in the cell when light is incident on the semiconductor

electrode:

1 . Photo generation of charge carriers (electron and hole pairs)

-> 2e" + 2h +

Semiconductor

2. Charge separation and migration of the holes to the interface between the
semiconductor and the electrolyte and of electrons to the counter electrode through the
external circuit. Now, holes are simply vacancies created in the valence band due to
promotion of electrons from the valence band to the conduction band. However, in the
study of electronic behavior of materials, "holes" are considered to be independent
entities, with their own mass.

238 Hydrogen Production

3. The holes move to the interface and react with water producing oxygen:

2 h + + H 2 ► 0.5 2(gas) + 2 H + (aq)

4. The electrons travel in the external circuit and arrive at the interface between the
counter electrode (cathode) and electrolyte. There, they reduce the H + ions to H 2 :

2 e + 2 H ( a q) ► H2( gas )

The complete reaction is absorption of photon and splitting of water into hydrogen and
oxygen.The representation of the same process in band energy terms is shown in Fig. 7.

The cell depicted in Fig. 7 is a single photoelectrode type cell, with the anode being the
active photoelectrode. The lower band is the valence band of the n-type semiconductor,
while the upper band is the conduction band. The energy difference between the top of
valence band and the bottom of conduction band is termed as the band gap of
semiconductor, E g .
Some other configurations of the PEC cell are also possible:

1 . The semiconducting material may be a p-type material. In this case, it will act as photo
cathode, and reduction of H + ions to H 2 will take place at this electrode. The counter
electrode may be a metal in this case.

2. Both electrodes, the cathode and anode, are photoactive semiconducting materials. In
this case, the n-type electrode will act, as anode and favors oxidation of water to oxygen
and H + will take place at this electrode. The p-type electrode will act as cathode, where
F£ + ions will be reduced to H 2 .

An Introduction to Energy Sources

239

Incident
Light

Transparent \

conducting

glass

Semiconductor
electrode

Titania

conduction

band

Counter
electrode

2H +2e

Fermi energy

^7~| Hp + 2h+ 1- l/20 2 + 2H

1 Transparent
conducting
glass

Fig. 7. Operating principles of a photoelectrochemical cell

Photocatalytic hydrogen production:

Essentially the photocatalysed reactions have generated considerable interest after the
photocatalytic splitting of water on TiC^ electrodes was first demonstrated by Fujishima
and Honda in 1972. Subsequently, various kinds of photocatalysts have been employed
for hydrogen production and remediation of pollutants from water. Dispersed
heterogeneous semiconductor surface provides a fixed environment that influences the
chemical reactivity. Simultaneous oxidation and reduction reaction occurs on the surface
of the catalyst on photoexcitation. The other advantages are, easy separation of catalyst
after the reaction by centrifugation, availability of large surface area, low cost and
stability.

In heterogeneous photocatalytic systems, absorption of the light is an essential
requirement for successful photocatalysis. In addition, it should be stable at the reaction
conditions employed and it should be chemically inert. Among the available materials
like metals, semiconductors and insulators, the semiconductors have been used because

240

Hydrogen Production

the band gap of semiconductor is optimum, band edge positions are suitable for
oxidation/reduction of water and one can possibly use sunlight as energy source to excite
the electron from the valence band.

In addition to the favorable band gap and band positions, semiconductors are
inexpensive, non-toxic, easily recoverable and capable of retaining the catalytic activity.
Also, loading of metal on the semiconductor surface and coupling of two semiconductors
can increase the efficiency of the semiconductor photocatalysed reaction. Even though
the light absorption is essential, other parameters like band gap, surface area, crystal
phase, morphology, rate of interfacial charge transfer, carrier density and stability are
also essential for the observed photocatalytic activity.

Photocatalysis involves the initial absorption of photons by a semiconductor to excite
electrons from valence band to conduction band. This results in the formation of
electron-hole pair within semiconductor. Excitation and redox processes taking place in
semiconductor photocatalyst are shown in Fig. 8.

V/NHE
-1.0-

+ 1.0-

— HVHj

+2.0-

+ 3.0 "

Conduction

Band

Forbidden
Band

-\AAA/

Band Gap

Valence Band h \

v£

HjO

Fig. 8. Excitation and redox reactions in semiconductor

For efficient photocatalytic reaction the electron-hole pair recombination must be
suppressed. Either trapping the photogenerated electron or hole or both can lead to this.
The electron in the conduction band moves to the surface and reduction reaction takes
place either with adsorbed molecule or surface groups. Self-recombination with the hole
in the valence band depresses the activity of the semiconductor.

An Introduction to Energy Sources

241

The reduction and oxidation strength of the photoexcited electron and hole can be
measured from the energy of the lower edge of the conduction band and upper edge of
the valence band. Depending on the relative positions of the top of valence band, bottom
of conduction band and the redox potentials of the species, the oxidation and reduction
processes are promoted.

[NHEJ

-1
P
O

1°

I 1

(V)2H

ZnS

TiO,

ZnO

CdS

3.2

2.5

3.2

3.6

wo, Sr ™*

3.2

Fe 2 3

2.2 3.2

H/H 2
-H 2 0/0 2

Fig. 9. Energy levels of various semiconductors

In general, the selection of semiconductor for a particular reaction is based on the
position of the valence and conduction band edges and redox potential of the adsorbed
species of interest, stability towards photocorrosion and the value of bandgap. Bandgaps
and energy levels of various semiconductors are shown in Fig. 9. To reduce water, the
potential of the bottom of conduction band must be more negative than the hydrogen
reduction potential; for oxidation reaction, the top of valence band should be more
positive than the oxidation potential of water; Energies of various semiconductors are
shown in the Fig. 9. with respect to normal hydrogen electrode (NHE).
Since the energy of valence and conduction levels of TiC>2 is optimum to oxidize most of
the organic species, and its high oxidation ability of photogenerated holes (E = 2.9V vs
NHE at pH = 0) makes it as the best choice for photo-catalyst. In addition TiC>2 is inert,
resistant to photocorrosion, thus making it as a good photo-catalyst. Among three
structural modifications of TiC>2 (brookite, rutile and anatase), anatase is the form that is
active. Even though there are other semiconductors to fulfill these criteria; some of them

242

Hydrogen Production

suffer from "photocorrosion" under the experimental conditions employed. Fig. 10
shows the typical photocatalytic water splitting setup.

Medium pressure Hg lamp

Cooling water ^?

Solution

Magnetic stirrer

Membrane

a"/ 3

Glass gas trap

ir\

Fig. 10. Photocatalytic water splitting setup

The major problem associated with photocatalytic splitting of water is the higher bandgap
of the available semiconductor materials like TiC>2. Because of the higher bandgap, these
materials require UV light irradiation for carrying out the reaction whereas sunlight
contains only 5% of UV radiation. The remaining part of the solar spectrum is composed
mainly of visible and IR radiation. Research now focuses on reducing the bandgap of the
available materials by various methods and finding new photoactive materials with lower
bandgap.
Summary

Even though there are various methods available, the processes like direct electrolysis,
steam methane reformation, biomass gasification, and hydrogen from coal and
thermochemical decomposition they require other forms of energy like heat and/or
electricity which can be obtained from fossil fuels or other expensive methods like
nuclear energy. Also some of the methods lead to evolution of green house gases like
carbon dioxide. Methods like photochemical hydrogen production have very less
quantum efficiency.

An Introduction to Energy Sources 243

Only the processes like photoelectrochemical, photocatalytic and biochemical hydrogen
production have the potential to replace fossil fuels. For that an effective semiconductor
photocatalyst, which has the desired bandgap, which absorbs light in the visible region,
needs to be developed. The biochemical methods are highly sensitive to the environment
and needs to be optimized for working under normal atmospheric conditions. Current
research has shown more progress in this field and hopefully we will see some methods
in future, which will produce hydrogen with completely renewable sources without any
emission of polluting gases.
References

1. R. Narayanan, B. Viswanathan, "Chemical and Electrochemical Energy Systems",
University Press, 1998.

2. www.rmi.org/sitepages/pid557.php

3. atom.ecn.purdue.edu/~vurade/PEC%20Generation%20of%20Hydrogen/
Introduction%20to%20PEC%20hydrogen%20production.htm

4. www.fao.org/docrep/w724 1 e/w724 1 eOO.htm#Contents

5 . http ://web .mit. edu/~pweigele/www/being/content/how/bio .html

6. Tokio Ohta, "Solar-Hydrogen Energy Systems", Pergamon Press, 1979

Chapter - 14

HYDROGEN STORAGE AND ECONOMY

M. Sankaran
1. Introduction

The fossil fuels in the form of coal, oil, and natural gas have powered the human society
for few centuries. But continuing to power the world from fossil fuels threatens our
energy supply and puts enormous strains on the environment. Unfortunately, forecasts for
energy demands are not so encouraging, due to both the population growth rate and
energy predictions of future consumption (Fig.l). Hence a new renewable energy system
must be developed. These include solar energy, wind energy, tidal energy and nuclear
energy. A major problem with several of the renewable energy source is that they are
intermittent and their energy density is low. Thus, there is a need for an energy carrier
that can act both as a storage and transportation medium to connect the energy source to
the energy consumer.

40-

1P-

h
*
2

Wh.<i Id MQ|i "Lilian

i«fl ;ti» aun >*a

:-J.II

ENERGY COHSUHPHC*

i&M

1M0

13S0

20M

2050

21Q0

Fig.l. Scenarios for energy demand and population growth

An Introduction to Energy Sources 245

One promising alternative to fossil fuels is hydrogen. Hydrogen is the cleanest,
sustainable and renewable energy carrier. Although in many ways hydrogen is an
attractive replacement for fossil fuels, it does not occur in nature as the fuel H2. Rather, it
occurs in chemical compounds like water or hydrocarbons that must be chemically
transformed to yield H 2 . At present, most of the world's hydrogen is produced from
natural gas by a process called steam reforming. However, steam reforming does not
reduce the use of fossil fuels but rather shifts them from end use to an earlier production
step; and it still releases carbon to the environment in the form of CO2. Thus, to achieve
the benefits of the hydrogen economy, we must ultimately produce hydrogen from
non-fossil resources, such as water, using a renewable energy source. The other methods
by which hydrogen produced are electrolysis of water, photochemical method and
biochemical methods. But the major difficulty of utilizing hydrogen as fuel or energy
carrier has been the absence of a practical means for hydrogen storage. The storage of
hydrogen becomes the critical problem that the world faces today. Developing a high
density hydrogen storage system is an essential one, which is above 6.5 wt% and that can
release hydrogen at room temperature and atmospheric pressure, has been the focus and
the goal of researchers for years. The gap between the present state of the art in hydrogen
production, storage, and use and that needed for a competitive hydrogen economy is too
wide to bridge in incremental advances.
2. Hydrogen storage options

Depending on storage size and application, several types of hydrogen storage systems
may be available. This includes stationary large storage systems, stationary small storage
systems at the distribution, or final user, level; mobile storage systems for transport and
distribution including both large-capacity devices (such as a liquid hydrogen tanker -
bulk carrier) and small systems (such as a gaseous or liquid hydrogen truck trailer); and
vehicle tanks to store hydrogen used as fuel for road vehicles. Because of hydrogen's low
density, its storage always requires relatively large volumes and is associated with either
high pressures (thus requiring heavy vessels) or extremely low temperatures, and/or
combination with other materials (much heavier than hydrogen itself).

246 Hydrogen Storage and Economy

Large underground hydrogen storage

Underground storage of hydrogen in caverns, aquifers, depleted petroleum and natural
gas fields, and human-made caverns resulting from mining and other activities is likely to
be technologically and economically feasible. Hydrogen storage systems of the same type
and the same energy content will be more expensive by approximately a factor of three
than natural gas storage systems, due to hydrogen's lower volumetric heating value.
Above-ground pressurized gas storage systems

Pressurized gas storage systems are used today in natural gas business in various sizes
and pressure ranges from standard pressure cylinders (50 liters, 200 bar) to stationary
high-pressure containers (over 200 bar) or low-pressure spherical containers (>30,000 m 3 ,
12 to 16 bar). This application range will be similar for hydrogen storage.
Vehicular pressurized hydrogen tanks

Development of ultra-light but strong new composite materials has enabled storage of
hydrogen in automobiles. Pressure vessels that allow hydrogen storage at pressures
greater than 200 bars have been developed and used in automobiles. A storage density
higher than 0.05 kg of hydrogen per 1 kg of total weight is easily achievable.
These options are viable for the stationary consumption of hydrogen in large plants that
can accommodate large weights and volumes. Storage as liquid H 2 imposes severe energy
costs because up to 40% of its energy content can be lost to liquefaction. The storage
containers lose energy due the boil-off of hydrogen that is caused by thermal
conductivity. The boil-off losses vary from 0.06 % per day of large containers to 3 % per
day of small vessels. The boil-off losses can be reduced through proper insulation.
For transportation use, the onboard storage of hydrogen is a far more difficult challenge.
Both weight and volume are at a premium, and sufficient fuel must be stored to make it
practical to drive distances comparable to gas powered cars. Meeting the volume
restrictions in cars or trucks, for instance, requires using hydrogen stored at densities
higher than its liquid density. Fig. 2. shows the volume density of hydrogen stored in
several compounds and in some liquid hydrocarbons.

An Introduction to Energy Sources

247

Density: 5 g

=nr 3 £ S cm -3

1 g cm"3

0.7 g cnr 3

160 -

/■

EMMS! •C" Hn °H 0igs

BaReH 5

14-0

«373 K, l bar

LiBH„

■

120 -

dec. M3K

C e H, a ^:,-'' *

H 3 chemieorbsd
Off carbon

■ '

% 100 -

SSO^S / a" . ■' 4 ctec.*mJc''

C^,ft lb » >/

b.p. 112K

b.p, 272 K

_^^^_

g w

NaAIH, ..-■

,' / dec. >52Crk .--''

** 60 -

H^physisoi-bfld
on carbon

40 -

20 -

10 15

p ra <Hj) (maaa%)

£5

Fig. 2. Stored hydrogen per mass and per volume (Comparison of metal hydrides, carbon
nanotubes, petrol and other hydrocarbons).

The most effective storage media are located in the upper right quadrant of the figure,
where hydrogen is combined with light elements like lithium, nitrogen, and carbon. The
materials in that part of the plot have the highest mass fraction and volume density of
hydrogen. Hydrocarbons like methanol and octane are notable as high volume density
hydrogen storage compounds as well as high energy density fuels, and cycles that allow
the fossil fuels to release and recapture their hydrogen are already in use in stationary
chemical processing plants.
3. Metal Hydrides

Metal hydrides are composed of metal atoms that constitute of a host lattice and hydrogen
atoms that are trapped in interstitial sites, such as lattice defects. The trap site can be a
vacancy or a line defect. In the case of a line defect, a string of hydrogen atoms may
accumulate along the defect. Such a string increases the lattice stress, especially if two
adjacent atoms recombine to form molecular hydrogen. Since adsorption of hydrogen
increases the size of lattices the metal is usually ground to a powder in order to prevent
the decrepitation of metal particles. There are two possible ways of hydriding a metal,

248

Hydrogen Storage and Economy

direct dissociative chemisorption and electrochemical splitting of water. These reactions

are, respectively

M + X/2H2 ► MH X and

M + x/2H 2 + x/2e" ►MH x + x/2 0H"

Where M represents the metal. In electrochemical splitting there has to be a catalyst, such

as palladium, to break down the water.

Hj GflS INTERFACE ME1AL

Q
00

(

r—

ZLtx

,.---sft'

I \ \

J - "

I \

_,-■"

'/■

..;..,•■".

.-■"*

-Ci

Fig. 3. a) Schematic of hydrogen chemisorption on metal, b) Potential wells of molecular
and atomic hydrogen

A schematic of hydrogen chemisorption is shown in Fig. 3a. As shown in the figure, the
molecular hydrogen reaches a shallow potential minimum near the surface and the atomic
hydrogen a deeper minimum almost at the surface. In the metal lattice hydrogen has
periodic potential minimums in the interstitial sites of metal lattice. This behavior is
explained below and is visualized in Fig. 3b. As a hydrogen molecule approaches the
metal surface, weak van der Waal's forces begin to act upon it drawing it closer. The
molecule reaches the potential well Ep at distance zp, and very large forces would be
required to force it any closer the surface in a molecular form. However, the dissociation
energy of hydrogen molecule is exceeded by the chemisorption energy. Thus the
hydrogen molecule dissociates and individual hydrogen atoms are attracted to the surface
by chemisorptive forces and they reach the potential well ECH. From this point
sometimes even the ambient temperature's thermal energy is enough to increase the

An Introduction to Energy Sources

249

vibrational amplitude of hydrogen atoms which can thus reach and enter the metal

surface.

Metal and hydrogen usually form two different kinds of hydrides, a-phase and p- phase

hydride. In a-phase there is only some hydrogen adsorbed and in p-phase the hydride is

fully formed. For example, Mg2Ni forms hydrides of Mg2NiHo.3 and Mg2NiH4. When

initially charged the hydride gets to the a-phase and after that when charged and

discharged the hydride usually undergoes the phase transformation such as

Mg 2 NiH . 3 + 3.7H

-> Mg 2 NiH 4

Fig. 4. Schematic of phase transition in metal hydride

A schematic of phase transition is presented in Fig. 4. When charging, hydrogen diffuses
from the surface of the particle through the P-phase to the phase-transition interface and
forms additional P-phase hydride. When discharging, hydrogen from the phase-transition
interface diffuses through the a-phase to the surface of the particle where it is
recombined into the form of molecular hydrogen. A study of nano-scaled particles shows
that when the metal grains are in the range of 5 to 50 nm, the kinetics of both absorption
and desorption is improved by an order of magnitude because of improved thermal
conductivity. The kinetics can also be improved with a catalyst. These catalysts can be in
liquid or solid form, but because the catalyst does not affect the overall reaction, its

250

Hydrogen Storage and Economy

amount should be kept as low as possible in order to keep the storage capacity sufficient.
In Fig. 5. the effects of the nanostructure and catalyst on the hydrogen adsorption of LaNis
is shown.

1 1 1
c

1
b

:-:■

T /--

-1

f /

K 3

LaNi 5 H x

20 40 60 ao

t(inm)

100

Fig. 5. Rate of hydrogen adsorption by LaNis . a) Polycrystalline, b) Nano-crystalline, c)
Nanocrystalline with catalyst

The most common characterization method of a metal hydride is the PCT (pressure -
concentration - temperature) curve in a form of P - C isotherms. A theoretical P - C
isotherm with a- and P-phases is shown in Figure 5. The concentration, i.e. the hydrogen
capacity, is usually defined as hydrogen atoms per metal molecule H/M. In order to
characterize the metal hydride it is convenient to use the maximum hydrogen capacity
(H/M)max. The reversible capacity A (H/M), defined as the plateau width, is also a useful
tool when considering the engineering capacities of metal hydrides.
The thermodynamic reaction equilibrium is defined with the equilibrium constant K

RT In K = AH - TAS
Where AH is the reaction enthalpy and AS the reaction entropy. For a solid-gas reaction
the equilibrium constant reduces to the pressure of the gas. Thus the van't Hoff equation
is obtained

InP =AH / RT - AS / R
Plotting the equilibrium (P, T)-values on In P versus 1/T scale gives the van't Hoff plot.
The reaction enthalpy can be derived from the angular coefficient of the plot with the
help of Equation and the plot tells the suitability of P - T behavior of a hydride for

An Introduction to Energy Sources

251

practical applications. The theoretical van't Hoff plot usually describes very well the real
properties of metal hydrides.

2 04 6 0-8
C H {HfMj

1-0 2-4 2-B 32 36

f M0" 3 K" 1 )

Fig. 6. Pressure composition isotherms for hydrogen absorption in a typical metal hydride.
In the Figure the solid solution (a-phase), the hydride phase ((3-phase) and the region of
the co-existence of the two phases are shown. The co-existence region is characterized by
the flat plateau and ends at the critical temperature Tc. The construction of the van't Hoff
plot is shown on the right hand side. The slope of the line is equal to the enthalpy of
formation divided by the gas constant and the intercept is equal to the entropy of
formation divided by the gas constant

The reaction enthalpy of hydride formation is an important quantity. It is usually negative
so the reaction is exothermic and thus the hydride formation releases energy. Therefore
the dehydration needs energy to be able to take place. Since most of the applications are
used in ambient temperature, or at least in the range of - 100 °C, the reaction enthalpy
should be quite small so that the hydride could take heat from the surroundings when
releasing hydrogen. In some fuel cell systems the hydride can take heat directly from the
fuel cell. The reaction enthalpy also affects directly the stability of a hydride since the gas
pressure is exponentially proportional to it. The essential requirements that should be
satisfied by metal hydrides proposed for hydrogen storage at a commercial level. These
are summarized below.

• High hydrogen content

• Facile reversibility of formation and decomposition reactions. The hydride should
be decomposable at moderate temperatures that can be provided from locally
available heat sources, like solar, automobile exhaust and waste heat sources

252

Hydrogen Storage and Economy

Absorption-desorption kinetics should be compatible with the charge-discharge

requirements of the system

The equilibrium dissociation pressure of the hydride at peak desorption rate

should be compatible with the safety requirements of the hydride containment

system. The hydride itself should have a high safety factor

The hydride should have a sufficient chemical and dimensional stability to permit

its being unchanged over a large number of charge-discharge cycles

Minimal hysteresis in adsorption-desorption isotherms

The hydride should be reasonably resistant to deactivation by low concentrations

of common (sometimes unavoidable) contaminants such as 02,H20,C02, CO,

and others

The total cost of hydride (raw materials, processing and production) should be

affordable for the intended application. The long term availability of raw

materials (that is, the metal resources), must be ensured. The cost of the hydride

system (which includes its containment) per unit of reversibly stored hydrogen

should be as low as possible

The storage vessel and ancillary equipment cost and the fabrication and

installation costs should be moderate

Operating and maintenance costs and purchased energy requirements (that is,

energy other than waste energy and energy extracted from the ambient air) per

storage cycle should be low.

Table 1. Hydrogen Storage capacity of metallic and intermetallic systems.

Material

Pdes(atm)

T(K)

H-atoms/
cm 3 (xl0 22 )

Weight % of
hydrogen

MgH 2

-10-6

552

6.5

7.6

Mg 2 NiH 4

-10-5

528

5.9

3.6

FeTiH 2

4.1

265

6.0

1.89

LaNi 5 H 6

1.8

285

5.5

1.37

An Introduction to Energy Sources 253

A judicious combination of technical and economic considerations will determine the
suitability of a hydride product for a given hydrogen storage or hydrogen containment
application. Hydrogen storage capacity of some of the metal and intermetallics are given
in Table 1 .

Metal hydrides are very effective at storing large amounts of hydrogen in a safe and
compact way. All the reversible hydrides working around ambient temperature and
atmospheric pressure consist of transition metals; therefore, the gravimetric hydrogen
density is limited to less than 3 mass%. It remains a challenge to explore the properties of
the lightweight metal hydrides.

4. Hydride Complexes

Certain transition metals form a hydride with some elements from the periodic table
groups IA and IIA when hydrogen is present. The transition metal stabilizes the complex
of hydrogen. For example, Mg2NiH4 is formed when Mg donates two electrons to the
[NiH/t] -4 complex. The kinetics of hydride complexes tends to be slower compared to the
traditional interstitial hydrides since the formation and decomposition of the hydride
complex requires some metal atom diffusion. Hydrogen desorption also needs usually
quite high temperatures (over 150 °C). Despite these disadvantages the high hydrogen
capacity makes these materials potential for hydrogen storage. For example, the
maximum capacity of Mg2FeH6 is 5.5 wt%. Also some non-transition metals form
complex hydrides. These includes, for example, reversible two-step reaction of NaAlHi

NaAlH 4 ► l / 3 Na 3 AlH 6 + 2 /3 Al + H 2 ► NaH + Al + 3 / 2 H 2

The maximum hydrogen capacity of this reaction is 5.6 wt%. When catalyzed with a
small amount of some liquid alkoxides the hydrogen pressure of 1 atm was obtained at 33
°C. The cyclic stability of reversible capacity was however very poor because the
catalysts brought impurities into the hydride. The latest studies show that with some
inorganic catalysts almost the theoretical reversible capacity of 5.6 wt% may be achieved.

5. Hydrogen in Carbon Structures

Hydrogen can be stored into the nanotubes by chemisorption or physisorption. The
methods of trapping hydrogen are not known very accurately but density functional
calculations have shown some insights into the mechanisms. Calculations indicate that
hydrogen can be adsorbed at the exterior of the tube wall by H-C bonds with a H/C

254

Hydrogen Storage and Economy

coverage 1.0 or inside the tube by H-H bonds with a coverage up to 2.4 as shown in
Figure 7. The adsorption into the interior wall of the tube is also possible but not stable.
The hydrogen relaxes inside the tube forming H-H bonds. The numbers in the figure tell
the bond lengths in 10" 10 m.

1.5D

6 a

1.53

Fig. 7. Hydrogen adsorption in a nanotube. a) exterior adsorption with H/C coverage 1.0,
b) interior adsorption with coverage 1.0, c) interior adsorption with coverage 1.2, d)
interior adsorption with coverage 2.4

Multi-walled nanotubes, in which two or more single tubes are rounded up each other
with van der Waal's attraction, can adsorb hydrogen between the single-wall nanotubes.
The hydrogen causes the radius of the tubes to increase and thus makes a multi-walled
nanotube less stable. In nanotube bundles hydrogen can also be adsorbed in the middle of
different tubes. The density functional calculations have shown that theoretically in
proper conditions a single-walled nanotube can adsorb over 14 wt% and a multi- walled
nanotube about 7.7 wt% of hydrogen. Dillon et al. reported the first experimental result
of high hydrogen uptake by a nanotube. They estimated that hydrogen could achieve a
density of 5 - 10 wt%. Chen et al. reported that alkali doped nanotubes are able to store
even 20 wt% under ambient pressure, but are unstable or require elevated temperatures.
The result has shown to be in a great disagreement with other results and has been
thought to be incorrect.

Recent results on hydrogen uptake of single- walled nanotubes are promising. At 0.67 bar
and 600 K about 7 wt% of hydrogen have been adsorbed and desorbed with a good
cycling stability. Another result at ambient temperature and pressure shows that 3.3 wt%

An Introduction to Energy Sources 255

can be adsorbed and desorbed reproducibly and 4.2 wt% with a slight heating. The price
of commercial nanotubes is quite high. Even though the price of the nanotubes is still
high they have a good potential in storing hydrogen. When the manufacturing techniques
are improved and some engineering problems solved, they may be highly competitive
against other hydrogen storage technologies.
Other Forms of Carbon

There are also some other forms of carbon that adsorb hydrogen. These are graphite
nanofibers, fullerenes, and activated carbon. All the three of these are briefly discussed.
5.1 Graphite Nanofibers

Graphite nanofibers are graphite sheets perfectly arranged in a parallel ('platelet'
structure), perpendicular ('tubular' structure), or at angle orientation ('herringbone'
structure) with respect to the fiber axis. A schematic of the structure of a nanofiber with
some hydrogen adsorbed between the sheets is represented in Fig. 8.

0.3* nm

Fig. 8. Schematic of graphite nanofiber with hydrogen adsorbed

The most critical factor affecting the hydrogen adsorption of nanofibers is the demand for
high surface area since the hydrogen is adsorbed in the middle of the graphite sheets.
Rodriguez et al. has reported that some nanofibers can adsorb over 40 - 65 wt% of
hydrogen. However, these results have been criticized and have not been able to be
reproduced. Studies have shown only about 0.7 - 1.5 wt% of hydrogen adsorbed in a
nanofiber under ambient temperature and pressures slightly above 100 bar Some other
studies claim that about 10-15 wt% of hydrogen have been adsorbed in graphitic and

256 Hydrogen Storage and Economy

non-graphitic carbon nanofibers. The cyclic stability and other properties of nanofibers
are not really studied yet and thus it is difficult to say whether the nanofibers will be
competitive against other hydrogen storage technologies or not.

5.2 Fullerenes

Fullerenes are synthesized carbon molecules usually shaped like a football, such as Ceo
and Cyo- Fullerenes are able to hydrogenate through the reaction.
C 6 o + xH 2 + xe" - -» C6oH x + xOH"

According to theoretical calculations the most stable of these are C 6 oH 2 4, C6oH 36 , and
C6oH 48 , latter of which is equal to 6.3 wt% of hydrogen adsorbed. An experimental study
made by Chen et al. shows that more than 6 wt% of hydrogen can be adsorbed on
fullerenes at 180 °C and at about 25 bar. Usually the bonds between C and H atoms are
so strong that temperatures over 400 °C are needed to desorb the hydrogen [40], but Chen
et al. were able to do this at a temperature below 225 °C. Despite the quite high hydrogen
storing ability, the cyclic tests of fullerenes have shown poor properties of storing
hydrogen.

5.3 Activated Carbon

Bulky carbon with high surface area, so-called activated carbon, is able to adsorb
hydrogen in its macroscopic pores. The main problems are that only some of the pores
are small enough to catch the hydrogen atom and that high pressure must be applied in
order to get the hydrogen into the pore. About 5.2 wt% of hydrogen adsorbed into the
activated carbon has been achieved at cryogenic temperatures and in pressures of about
45 - 60 bar. In ambient temperature and pressure of 60 bar the figure has been only
approximately 0.5 wt%. Some studies show that a combination of carbon-adsorbent in a
pressure vessel can adsorb little more hydrogen than what would fit into an empty vessel
as gas. This is true for pressures below about 150 bar after which an empty vessel can
store more hydrogen. The poor P - T properties for hydrogen sorption of activated carbon
prevents them from being suitable hydrogen storage in practical applications.
6. Zeolites

Zeolites are microporous inorganic compounds with an effective pore size of about 0.3 -
1 .0 nm. The pore size is sufficient to permit the diffusion of some small molecules, such

An Introduction to Energy Sources 257

as hydrogen, under elevated temperatures and pressures. However, most of the pores are
smaller than the kinetic size of a hydrogen molecule in ambient temperature. Thus
reducing the temperature the hydrogen is trapped into the cavities of the molecular sieve
host. Zeolites have structures based on TO4 tetrahedra, where T is a silicon or aluminum
atom. Depending on the structure, Si / Al - ratio, and substituting atoms, such as Na, K,
and Pd, the zeolites are named as zeolite A, X, Y, or mordenites etc. An example of the
pore structure (big holes) of zeolites is given in Fig. 9.

Fig. 9. Pore structure of zeolites, a) Side view, b) Top view

The hydrogen storage capacity of zeolites is quite poor. At temperatures of 200 - 300°C
and pressures of about 100 - 600 bar about 0.1 - 0.8 wt% of hydrogen is adsorbed. The
cyclic stability of zeolites has not been really studied. Ernst et al. suggested that by
applying sophisticated techniques of synthesis and modification there may exist a
potential in zeolites. However, this is yet to be seen.
7. Glass Spheres

Glass spheres are small hollow glass micro-balloons whose diameter vary from about 25
mm to 500 mm and whose wall thickness is about 1 mm. The spheres are filled with
hydrogen at high pressure and temperature of 200 - 400 °C. High temperature makes the
glass wall permeable and the hydrogen is able to fill in. Once the glass is cooled down to
ambient temperature, the hydrogen is trapped inside the spheres. The hydrogen can be
released by heating or crushing the spheres. The crushing naturally prevents the reuse of
spheres and is not necessarily a very favorable option. The glass spheres can also cause

258 Hydrogen Storage and Economy

accidents when breaking down if not handled properly. The storage capacity of spheres is
about 5-6 wt% at 200 - 490 bar.

8. Chemical Storage

Chemical compounds containing hydrogen can also be considered as a kind of hydrogen
storage. These include e.g. methanol CH2OH, ammonia NH3, and methylcyclohexane
CH3C6H12. In STP condition all of these compounds are in liquid form and thus the
infrastructure for gasoline could be used for transportation and storage of the compounds.
This is a clear advantage compared to gaseous hydrogen, which demands leak-proof,
preferably seamless, piping and vessels. The hydrogen storage capacity of these chemical
compounds is quite good - 8.9 wt% for CH 2 OH, 15.1 wt% for NH 3 , and 13.2 wt% for
CH3C6H12. These figures do not include the containers in which the liquids are stored.
Because the containers can be made of light- weighted composites or even plastic in some
cases, the effect of a container is negligible especially with larger systems.
Chemical storage of hydrogen has also some disadvantages. The storage method is non-
reversible, i.e. the compounds cannot be "charged" with hydrogen reproducibly. The
compounds must be produced in a centralized plant and the reaction products have to be
recycled somehow. This is difficult especially with ammonia, which produces highly
pollutant and environmentally unfavorable nitrogen oxides. Other compounds produce
carbon oxides, which are also quite unfavorable.

9. Summary of Hydrogen Storage Technologies

The hydrogen storage capacities of different storage methods in weight per cents and
corresponding hydrogen energy capacities in kWh/kg are gathered in Table. The
capacities shown in the table are the maximum values that are experimentally achieved.
For metal hydrides and nanotubes, the lower values are in practical conditions and greater
the maximum values in elevated temperatures and / or pressures. Also some possible
application areas for different storage methods are gathered in Table. These are portable
(PO), transportation (TR), and power production (CHP), and are discussed in the next
chapter. There is no specific application area marked for activated carbon, zeolites, or
glass spheres because of the unpractical operating conditions or poor hydrogen storage
capacity. Some special applications, in which high temperatures and pressures are used,

An Introduction to Energy Sources

259

may exist for activated carbon and glass spheres. Carbon nanostructures are thought to
have potential for portable and transportation applications in the future.

Table 2. Hydrogen capacities of different storage methods

Storage method

Hydrogen
capacity (Wt %)

Energy capacity
(KW/Kg)

Possible
application areas

Gaseous H 2

11.3

6.0

TR*, CHP

Liquid H 2

25.9

13.8

Metal hydrides

-2-6.6

0.8-2.3

PCf , TR

Activated carbon

6.2

2.2

Zeolites

0.8

Glass spheres

2.6

Nanotubes

4.2-7

1.7-3.0

PO,TR

Fullerenes

2.5

PO,TR

Chemical

8.9-15.1

3.8-7.0

All

*TR - Transport
**PO - Portable applications

10. Hydrogen economy

It may be that Hydrogen economy has the potential of being a reality but all the three
stages of hydrogen economy namely hydrogen production, storage and transportation
infrastructure are still in the initial stages of development and certainly need considerable
scientific input. The realization of this hydrogen economy largely depends on the
cooperation between the scientists for the development of new materials and
technologists to design appropriate devices and reactors so that this alternate form of
energy source can be utilized by mankind. A comprehensive delivery infrastructure for
hydrogen faces many scientific, engineering, environmental, safety and market
challenges.

The public acceptance of hydrogen depends not only on its practical and commercial
appeal, but also on its record of safety in widespread use. The flammability, buoyancy,
and permeability of hydrogen present challenges to its safe use. These properties are
different from, but not necessarily more difficult than, those of other energy carriers. Key

260

Hydrogen Storage and Economy

to public acceptance of hydrogen is the development of safety standards and practices

that are widely known and routinely used like those for self service gasoline stations or

plug in electrical appliances. The technical and educational components of this aspect of

the hydrogen economy need careful attention. Achieving these technological milestones,

while satisfying the market discipline of competitive cost, performance, and reliability,

requires technical breakthroughs that come only from basic research.

Cooperation among nations to leverage resources and create innovative technical and

organizational approaches to the hydrogen economy is likely to significantly enhance the

effectiveness of any nation that would otherwise act alone. The emphasis of the hydrogen

research agenda varies with country; communication and cooperation to share research

plans and results are essential.

11. Economics and development patterns

The development of hydrogen storage device is the critical component:

Table 3. Summary of the hydrogen storage costs for stationary applications

Storage System /

Specific TCI

Storage Cost

Size ( GJ)

^U>/vjJ capacity/

($/GJ)

Compressed Gas

Short term (1-3 days)

131

9,008

4.21

147

16,600

33.00

13,100

2,992

1.99

20,300

2,285

1.84

130,600

1,726

1.53

Long term (30 days)

3,900

3,235

36.93

391,900

1,028

12.34

3,919,000

580

7.35

Liquefied Hydrogen

Short term (1-3 days)

131

35,649

17.12

13,100

7,200

6.68

An Introduction to Energy Sources

261

20,300

1,827

5.13

130,600

3,235

5.26

Long term (30 days)

3,900

1,687

22.81

108,000

1,055

25.34

391,900

363

8.09

3,919,000

169

5.93

Metal Hydride

Short term (1-3)

131-130,600

4,191-18,372,

2.89-7.46

Long term (30 days)

3,900-3.9 million

18,372

205.31

Cryogenic Carbon (1 day)

4,270

26.63

Underground (1-day)

7-1,679

1.00-5.00

Carbon nanostructure systems are expected to have significantly reduced costs because
there is no cryogenic requirement, but the technology is still in the early development
stages and so costs have not yet been developed. Currently, there are no commercial
applications of carbon-based hydrogen storage. However, researchers are continuing to
look into increasing the gravimetric capacity of these systems and to improve the overall
system engineering.
12. Forecasting

Essentially the challenges that have to be faced in the development of suitable hydrogen
storage medium are:

• Reducing the cost of production of hydrogen storage medium like carbon
nano tubes using economical methods.

• The existing demand prohibits development of high storage capacity facilities.

• The simultaneous utilization of storage medium as electrode as well the hydrogen
storage medium, by then the hydrogen released can be effectively utilized.

• High storage capacity of hydrogen by any of the possible methods needs
considerable development of the relevant technology.

262 Hydrogen Storage and Economy

13. Global demands and infrastructure

Demand for alternative energy increase as increase in the energy requirement. The
drawback of utilizing hydrogen as the alternative fuel is mainly due to the absence of the
appropriate storage medium.

• The challenges and demand faced for the storage of hydrogen can be surmounted
if the following aspects are addressed

• Investigation and development of new materials for the storage of hydrogen.

• One has to develop suitable and reproducible experimental techniques to identify
the storage capacity.

• International / National awareness should be increased in both hydrogen based
technology and the possibility of developing such technology.

• The existing storage medium can be improved considerably and the cost and size
of the storage medium can also be reduced.

• Steps towards hydrogen economy

• The steps towards the hydrogen-based economy must include the following:

• The hydrogen-based economy will and can reduce our dependence on fossil fuels
and also tilt our economy from the anxiety over foreign exchange reserve.

• It will have considerable environmental acceptance and also reduce the strain the
country is facing today in some major cities.

• There must be governmental and non-governmental will power to initiate,
implement and sustain the programme, overcoming the teething issues that may
arise out of this transition.

• Enough resources have to be generated and utilized in a profitable and also non-
wasteful manner in order to achieve the objectives

In order to realize this vision for a hydrogen based economy, the country needs a national
road map for hydrogen energy comprising in total all the aspects of hydrogen energy as
outlined above and also the social acceptance and adaptation.

14. Recommendations:

Skills of all nature are required for such a development and it is essential the following
aspects be immediately considered.

• Development of highly efficient storage medium

An Introduction to Energy Sources 263

• Development of cost effective materials with considerable cycles life time

• Development of suitable engineering design and also the subsequent power
converters.

• Principles for production, materials for storage and also the necessary infra
structure.

• The policies governing energy, environmental concerns, utility regulations,
business opportunities, the moral and social codes and practices and the standards
of living we expect are the critical elements of an appropriate infra structure in
which the Hydrogen energy based economy can develop.

The participating organizations, namely government, industry, academic and research
institutions, environmental agencies should work together with zeal to execute the top
priority actions and recommendations in the true spirit of participation and cooperation.
References

1. Christmann K., Hydrogen Adsorption on Metal Surfaces. In: Atomistics of
Fracture Conference Proceedings, Eds. Latanision and Pickensr, Plenum, NY,
USA 1981

2. Sandrock G., A Panoramic Overview of Hydrogen Storage Alloys from a Gas
Reaction Point of View, J. Alloys and Compounds, Vol. 293-295, pp. 877- 888,
1999

3. Lee S., Lee Y., Hydrogen Storage in Single-Walled Carbon Nanotubes, Applied
Physics Letters, Vol. 76, No. 20, pp. 2877-2899, 2000

4. J. Bockris, Hydrogen economy in the future, International Journal of Hydrogen
Energy 24 (1999), pp. 1-15.

5. Maria H. Maack and Jon Bjorn Skulason, Implementing the hydrogen economy
Journal of Cleaner Production Volume 14, Issue 1 , 2006, Pages 52- 64.

Chapter - 15

BIOCHEMICAL ENERGY CONVERSION PROCESSES

C. M. Janet

1. Introduction

As we have assimilated almost all of the available options for the energy production,
conversion and utility, it is the right time for us to evaluate and understand how all these
energy conversion processes are significant over one or the other and how the disparity in all
can be perceived and corrected taking the principles of nature. Even though petroleum,
petrochemicals, coal, fossil fuels are efficient, the amount of hazardous byproducts released to
the atmosphere is a matter of concern. Nuclear energy seems to be promising and attractive,
but having the control over the process to provide enough security and safety appear to be
cumbersome. And about extracting the solar power for energy production by means of
photovoltaic and photoelectrochemical cells has not reached to the extent that the common man
can access it cheaply. Hence it is appropriate to go for nature's principles for the production
and processing of energy. Biochemical processes are having many advantages such as

1 . No unwanted and hazardous by-products are formed.

2. Occurs at normal temperatures and pressures

3. No special equipments are needed.

4. All are renewable energy sources

5. Eco friendly process

Green chemistry offers cleaner processes for energy abatement. Some of such energy
conversion processes are

1 . Photosynthesis

2. Glycolysis

3. Nitrogen fixation

4. Fermentation processes

2. Photosynthesis

Although some of the steps in photosynthesis are still not completely understood, the overall
photosynthetic reaction has been known since the 1800s. Jan van Helmont began the research

An Introduction to Energy Sources 265

of the process in the mid- 1600s when he carefully measured the mass of the soil used by a
plant and the mass of the plant as it grew. After noticing that the soil mass changed very little,
he hypothesized that the mass of the growing plant must come from the water, the only
substance he added to the potted plant. This was a partially accurate hypothesis - much of the
gained mass also comes from carbon dioxide as well as water. However, this was a point to
the idea that the bulk of a plant's biomass comes from the inputs of photosynthesis, not the soil
itself. Photosynthesis is an important biochemical process in which plants, algae, and some
bacteria harness the energy of sunlight to produce food. Ultimately, nearly all living things
depend on energy produced from photosynthesis for their nourishment, making it vital to life
on earth. It is also responsible for producing the oxygen that makes up a large portion of the
earth's atmosphere. Organisms that produce energy through photosynthesis are called
photoautotrophs. Half of all photosynthesis comes not from plants, but from bacteria and algae.
It is a process in which green plants utilize the energy of sunlight to manufacture carbohydrates
from carbon dioxide and water in the presence of chlorophyll. A vast majority of plants contain
chlorophyll — concentrated, in the higher land plants, in the leaves. In these plants water is
absorbed by the roots and carried to the leaves by the xylem, and carbon dioxide is obtained
from air that enters the leaves through the stomata and diffuses to the cells containing
chlorophyll. The green pigment chlorophyll is uniquely capable of converting the active energy
of light into a latent form that can be stored (in food) and used when needed.
2.1 Photosynthetic process

The initial process in photosynthesis is the decomposition of water (H2O) into oxygen and
hydrogen and oxygen will be released. Direct light is required for this process. The hydrogen
and the carbon and oxygen of carbon dioxide (CO2) are then converted into a series of
increasingly complex compounds that result finally in a stable organic compound, glucose
(C 6 Hi 2 6 ), and water. This phase of photosynthesis utilizes stored energy and therefore can
proceed in the dark.
The simplified equation of this overall process is

6CO2 + 12H 2 + energy ► C 6 H 12 6 + 60 2 + 6H 2

In general, the results of this process are the reverse of those in respiration, in which
carbohydrates are oxidized to release energy, with the production of carbon dioxide and water.
The intermediary reactions before glucose is formed involve several enzymes, which react with

266 Biochemical Energy Conversion Processes

the coenzyme ATP ( Adenosine Triphosphate) to produce various molecules. Studies using
radioactive carbon have indicated that among the intermediate products are three-carbon
molecules from which acids and amino acids, as well as glucose, are derived. This suggests
that fats and proteins are also products of photosynthesis. The main product, glucose, is the
fundamental building block of carbohydrates (e.g., sugars, starches, and cellulose). The water-
soluble sugars (e.g., sucrose and maltose) are used for immediate energy. The insoluble
starches are stored as tiny granules in various parts of the plant chiefly the leaves, roots
(including tubers), and fruits and can be broken down again when energy is needed. Cellulose
is used to build the rigid cell walls that are the principal supporting structure of plants.

2.2 Importance of Photosynthesis

Animals and plants both synthesize fats and proteins from carbohydrates; thus glucose is a basic
energy source for all living organisms. The oxygen released (with water vapor, in transpiration)
as a photosynthetic byproduct, principally of phytoplankton, provides most of the atmospheric
oxygen vital to respiration in plants and animals, and animals in turn produce carbon dioxide
necessary to plants. Photosynthesis can therefore be considered the ultimate source of life for
nearly all plants and animals by providing the source of energy that drives all their metabolic
processes. Green plants use the energy in sunlight to carry out chemical reactions, such as the
conversion of carbon dioxide into oxygen. Photosynthesis also produces the sugars that feed
the plant.

2.3 Plant photosynthesis

Plants are photoautotrophs, which mean they are able to synthesize food directly from
inorganic compounds using light energy, instead of eating other organisms or relying on
material derived from them. This is distinct from chemoautotrophs that do not depend on light
energy, but use energy from inorganic compounds. The energy for photosynthesis ultimately
comes from absorbed photons and involves a reducing agent, which is water in the case of
plants, releasing oxygen as a waste product. The light energy is converted to chemical energy,
in the form of ATP and NADPH, using the light-dependent reactions and is then available for
carbon fixation. Most notably plants use the chemical energy to fix carbon dioxide into
carbohydrates and other organic compounds through light-independent reactions. The overall
equation for photosynthesis in green plants is:
n C0 2 + 2n H 2 + light energy -> (CH 2 0)„ + n 2 + n H 2

An Introduction to Energy Sources 267

where n is defined according to the structure of the resulting carbohydrate. However, hexose
sugars and starch are the primary products, so the following generalized equation is often used
to represent photosynthesis:

6 C0 2 + 6 H 2 + light energy -> C 6 Hi 2 6 + 6 2
More specifically, photosynthetic reactions usually produce an intermediate product, which is
then converted to the final hexose carbohydrate products. These carbohydrate products are then
variously used to form other organic compounds, such as the building material cellulose, as
precursors for lipid and amino acid biosynthesis or as a fuel in cellular respiration. The latter
not only occurs in plants, but also in animals when the energy from plants get passed through a
food chain. In general outline, cellular respiration is the opposite of photosynthesis. Glucose
and other compounds are oxidized to produce carbon dioxide, water, and chemical energy.
However, both processes actually take place through a different sequence of reactions and in
different cellular compartments.

Plants capture light primarily using the pigment chlorophyll, which is the reason that most
plants have a green color. The function of chlorophyll is often supported by other accessory
pigments such as carotenoids and xanthophylls. Both chlorophyll and accessory pigments are
contained in organelles (compartments within the cell) called chloroplasts. Although all cells in
the green parts of a plant have chloroplasts, most of the energy is captured in the leaves. The
cells in the interior tissues of a leaf, called the mesophyll, contain about half a million
chloroplasts for every square millimeter of leaf. The surface of the leaf is uniformly coated
with a water-resistant, waxy cuticle, which protects the leaf from excessive evaporation of
water as well as decreasing the absorption of ultraviolet or blue light to reduce heating. The
transparent, colourless epidermis layer allows light to pass through to the palisade mesophyll
cells where most of the photosynthesis takes place. The light energy is converted to chemical
energy using the light-dependent reactions. The products of the light dependent reactions are
ATP from photophosphorylation and NADPH from photo reduction. Both are then utilized as
an energy source for the light-independent reactions.

268

Biochemical Energy Conversion Processes

accessory pigments

photosystem

primary pigment reaction
centre P700 or P680

thylakoid

Fig.l. A photosystem: a light-harvesting cluster of photosynthetic pigments in a
chloroplast thylakoid membrane

Key

-* flow of electrons in non-cyclic photophosphorylation

flow or electrons in cyclic photophosphorylation

chains of electron carriers

H,0

NADP + 2H +

reduced

NADP

increasing

energy
level

P6S0
photosystem II

light

Fig.2. The 'Z-scheme' of electron flow in light-dependent reactions
2.4 Z scheme

In plants, the light-dependent reactions occur in the thylakoid membranes of the
chloroplasts and use light energy to synthesize ATP and NADPH. The photons are
captured in the antenna complexes of photosystem I and II by chlorophyll and accessory
pigments. When a chorophyll a molecule at a photosystem's reaction center absorbs

An Introduction to Energy Sources 269

energy, an electron is excited and transferred to an electron-acceptor molecule through a
process called photo induced charge separation. These electrons are shuttled through an
electron transport chain that initially functions to generate a chemiosmotic potential
across the membrane, the so called Z-scheme shown in Fig. 2. An ATP synthase enzyme
uses the chemiosmotic potential to make ATP during photophosphorylation while
NADPH is a product of the terminal redox reaction in the Z-scheme.

2.5 Water photolysis

The NADPH is the main reducing agent in chloroplasts, which provides a source of
energetic electrons to other reactions. Its production leaves chlorophyll with a deficit of
electrons (oxidized), which must be obtained from some other reducing agent. The
excited electrons lost from chlorophyll in photosystem I are replaced from the electron
transport chain by plastocyanin. However, since photosystem II includes the first steps of
the Z-scheme, an external source of electrons is required to reduce its oxidized
chlorophyll a molecules. This role is played by water during a reaction known as
photolysis and results in water being split to give electrons, oxygen and hydrogen ions.
Photosystem II is the only known biological enzyme that carries out this oxidation of
water. Initially, the hydrogen ions from photolysis contribute to the chemiosmotic
potential but eventually they combine with the hydrogen carrier molecule NADP + to form
NADPH. Oxygen is a waste product of photosynthesis but it has a vital role for all
organisms that use it for cellular respiration.

2.6 Bioenergetics of photosynthesis

Photosynthesis is a physiological phenomenon that converts solar energy into
photochemical energy. This physiological phenomenon may be described
thermodynamically in terms of changes in energy, entropy and free energy. The energetic
of photosynthesis, driven by light, causes a change in entropy that in turn yields a usable
source of energy for the plant. The following chemical equation summarizes the products
and reactants of photosynthesis in the typical green photosynthesizing plant:
C0 2 + H 2 -> 2 + (CH 2 0) +112 kcal/mol C0 2

On earth, there are two sources of free energy: light energy from the sun, and terrestrial
sources, including volcanoes, hot springs and radioactivity of certain elements. The
biochemical value of electromagnetic radiation has led plants to use the free energy from

270 Biochemical Energy Conversion Processes

the sun in particular. Visible light, which is used specifically by green plants to
photosynthesize, may result in the formation of electronically excited states of certain
substances called pigments. For example, Chi a is a pigment which acts as a catalyst,
converting solar energy into photochemical energy that is necessary for photosynthesis.
With the presence of solar energy, the plant has a usable source of energy, which is
termed as the free energy (G) of the system. However, thermal energy is not completely
interconvertible, which means that the character of the solar energy may lead to the
limited convertibility of it into forms that may be used by the plant. This relates back to
the work of Josiah Willard Gibbs: the change in free energy (AG) is related to both the
change in entropy (AS) and the change in enthalpy (AH) of the system (Rabinowitch).
Gibbs free energy equation:

AG = AH - TAS
Past experiments have shown that the total energy produced by photosynthesis is 112
kcal/mol. However in the experiment, the free energy due to light was 120 kcal/mol. An
overall loss of 8 kcal/mol was due to entropy, as described by Gibbs equation. In other
words, since the usable energy of the system is related directly to the entropy and
temperature of the system, a smaller amount of thermal energy is available for conversion
into usable forms of energy (including mechanical and chemical) when entropy is great
(Rabinowitch). This concept relates back to the second law of thermodynamics in that an
increase in entropy is needed to convert light energy into energy suitable for the plant.
Overall, in conjunction with the oxidation-reduction reaction, nature of the
photosynthesis equation and the interrelationships between entropy and enthalpy, energy
in a usable form will be produced by the photosynthesizing green plant.
Energy and carbon are obtained by organisms either directly or indirectly via the
photosynthetic conversion of solar energy. These organisms have evolved metabolic
machineries for the photochemical reduction of carbon dioxide to organic matter and/or
for the subsequent utilization of the organics for biosynthesis and controlled energy
liberation. These metabolic routes can be exploited to provide fuels from biochemical
sources. The majority of the bioengineering strategies for biochemically derived fuels
involve options for the disposition of organic matter produced via photosynthate. The
bulk of the presently exploited photosynthate is directed toward the production of wood,

An Introduction to Energy Sources 271

food, and feed. During processing and consumption, waste organic materials are
generated which can be used for energy production via combustion, pyrolysis or
biochemical conversions to ethanol, hydrogen, methane, and isopropanol. A second
option is to engineer the photosynthetic apparatus to provide hydrogen. The third strategy
is the cultivation of crops as energy sources, i.e., the farming of an energy crop which can
be used as an energy source via the foregoing processes.

The photosynthetic apparatus and the mechanisms by which it operates have been
intensively investigated over the past 30 to 40 years. The current understanding is that it
consists of three series of interconnected oxidation-reduction reactions: The first involves
the evolution of oxygen from water. The second is the transfer of H atoms to a primary
hydrogen acceptor. The third is the reduction of CO2 to carbohydrates by the primary
hydrogen acceptor. The light energy required for photosynthesis is used to drive the H
atoms against the potential gradient. The photochemical stage of photosynthesis consists
of two separate steps, I and II. The products of light reaction II are an intermediate
oxidant and a strong oxidant which is capable of oxidizing water to oxygen. An
intermediate oxidant and a strong reductant that can reduce carbon dioxide are produced
in light reaction I. The two light reactions involve two pigment systems, photosystems I
and II, interconnected by enzymatic reactions coupled with photophosphorylation
yielding adenosine triphosphate (ATP). ATP is one of several high energy (7 to 8 kcal
liberated upon hydrolysis per mole) compounds used in biological systems for chemical
energy storage.
3. Glycolysis

It is a series of biochemical reactions by which a molecule of glucose is oxidized to two
molecules of pyruvic acid. The word glycolysis is from Greek glyk meaning sweet and
lysis meaning dissolving. It is the initial process of many pathways of carbohydrate
catabolism, and serves two principal functions: generation of high-energy molecules
(ATP and NADH), and production of a variety of six- or three-carbon intermediate
metabolites, which may be removed at various steps in the process for other intracellular
purposes (such as nucleotide biosynthesis). Glycolysis is one of the most universal
metabolic processes known, and occurs (with variations) in many types of cells in nearly
all types of organisms. Glycolysis alone produces less energy per glucose molecule than

272 Biochemical Energy Conversion Processes

complete aerobic oxidation, and so flux through the pathway is greater in anaerobic
conditions (i.e., in the absence of oxygen). The most common and well-known type of
glycolysis is the Embden-Meyerhof pathway, initially elucidated by Gustav Embden and
Otto Meyerhof. The term can be taken to include alternative pathways, such as the
Entner-Doudoroff Pathway. However, glycolysis will be used as a synonym for the
Embden-Meyerhof pathway. The overall reaction of glycolysis is:
Glc + 2 NAD + + 2 ADP + 2 P, -> 2 NADH + 2 Pyr + 2 ATP + 2 H 2 + 2 H +
So, for simple fermentations, the metabolism of 1 molecule of glucose has a net yield of 2
molecules of ATP. Cells performing respiration synthesize more ATP, but this is not
considered part of glycolysis proper, although these aerobic reactions do use the product
of glycolysis. Eukaryotic aerobic respiration produces an additional 34 molecules
(approximately) of ATP for each glucose molecule oxidized. Unlike most of the
molecules of ATP produced via aerobic respiration, those of glycolysis are produced by
substrate-level phosphorylation.
3.1 Biochemical oxidations

Respiration refers to those biochemical processes in which organisms oxidize organic
matter and extract the stored chemical energy needed for growth and reproduction.
Respiration patterns may be subdivided into two major groups, based on the nature of the
ultimate electron acceptor. Although alternative pathways exist for the oxidation of
various organic substrates, it is convenient to consider only the degradation of glucose.
(The metabolic routes provide the means for metabolism of pentoses and for
interconversions between sugars and other metabolites.) The breakdown of glucose is via
the Embden-Meyerof-Parnas glycolytic pathway which yields 2 moles each of pyruvate,
ATP, and reduced nicotinamide adenine dinucleotide (NAD) per mole of glucose. Under
aerobic conditions, the pyruvate is oxidized to CO2 and H 2 via the tricarboxylic acid or
Krebs cycle and the electron transport system. The net yield for glycolysis followed by
complete oxidation is 38 moles ATP per mole glucose, although there is evidence that the
yield for bacteria is 16 moles ATP per mole of glucose (Ref. 6). Thus, 673 kcal are
liberated per mole glucose, much of which is stored as ATP. Under anaerobic conditions,
various pathways exist for pyruvate metabolism which serves to reoxidize the reduced
hydrogen carriers formed during glycolysis. The ultimate acceptor builds up as a waste

An Introduction to Energy Sources

273

product in the culture medium. The end products of the pathways are: (1) CO2, ATP, and
acetate; (2) C0 2 and ethanol; (3) H 2 and C0 2 ; (4) C0 2 and 2, 3-butylene glycol; (5) C0 2 ,
H 2 , acetone, ATP, and butanol; (6) succinate; and (7) lactate. The pathway that occurs
depends on the microorganism cultivated and the culture. In terms of energy liberation,
the anaerobic fermentations are inherently inefficient. The end products of these
metabolic activities are reduced and possess high heats of combustion. Several examples
are shown in Table 1 . It is the value of these products for various purposes including
fuels which make the anaerobic oxidation of organic substrates attractive.

Table 1. Heats of combustion for theoretical oxidation of glucose by various routes are
shown as kcal p er mole of glucose fermented

Products

Heat of Combustion

2 C0 2 + 2 C 2 H 5 OH

654

2 Lactic acid

652

3 CH 4 + 3 C0 2

634

H 2 + C0 2

Lactic acid

654

Mixed acid (Escherichia)

633

4. Biological Nitrogen Fixation

Nitrogen fixation is the process by which nitrogen is taken from its relatively inert
molecular form (N 2 ) in the atmosphere and converted into nitrogen compounds useful for
other chemical processes (such as, notably, ammonia, nitrate and nitrogen dioxide).
Biological Nitrogen Fixation (BNF) is where atmospheric nitrogen is converted to
ammonia by a bacterial enzyme called nitrogenase. Microorganisms that fix nitrogen are
called diazotrophs. The formula for BNF is:

N 2 + 8H + + 8e" + 16 ATP -> 2NH 3 + H 2 + 16ADP + 16 P,
Although ammonia (NH3) is the direct product of this reaction, it is quickly ionized to
ammonium (NH/t + ) ions. In free-living diazotrophs, the nitrogenase-generated ammonium
ions are assimilated into glutamate through the glutamine synthetase/glutamate synthase
pathway. Biological nitrogen fixation was discovered by the Dutch microbiologist
Martinus Beijerinck.

274

Biochemical Energy Conversion Processes

Releue

J Nitrogen
Cycle

Fig. 3. Schematic representation of nitrogen cycle

4.1 Leguminous nitrogen-fixing plants

The best-known are legumes such as clover, which contain symbiotic bacteria called
rhizobia within nodules in their root systems, producing nitrogen compounds that help to
fertilize the soil. The great majority of legumes have this association, but a few genera
(e.g., Styphnolobium) do not.
5. Fermentation

The anaerobic conversion of sugar to carbon dioxide and alcohol by yeast is known as
Fermentation. Since fruits ferment naturally, fermentation precedes human history.
However, humans began to take control of the fermentation process at some point. There
is strong evidence that people were fermenting beverages in Babylon circa 5000 BC,
ancient Egypt circa 3000 BC, pre-Hispanic Mexico circa 2000 BC, and Sudan circa 1500
BC. There is also evidence of leavened bread in ancient Egypt circa 1500 BC and of milk
fermentation in Babylon circa 3000 BC. The Chinese were probably the first to develop
vegetable fermentation.

An Introduction to Energy Sources 275

Fermentation is a process by which the living cell is able to obtain energy through the
breakdown of glucose and other simple sugar molecules without requiring oxygen.
Fermentation is achieved by somewhat different chemical sequences in different species
of organisms. Two closely related paths of fermentation predominate for glucose. When
muscle tissue receives sufficient oxygen supply, it fully metabolizes its fuel glucose to
water and carbon dioxide. However, at times of strenuous activity, muscle tissue uses
oxygen faster than the blood can supply it. During this anaerobic condition, the six-
carbon glucose molecule is only partly broken down to two molecules of the three-carbon
sugar called lactic acid. This process, called lactic acid fermentation, also occurs in many
microorganisms and in the cells of higher animals. In alcoholic fermentation, such as
occurs in brewer's yeast and some bacteria, the production of lactic acid is bypassed, and
the glucose molecule is degraded to two molecules of the two-carbon alcohol, ethanol,
and to two molecules of carbon dioxide. Many of the enzymes of lactic acid and alcoholic
fermentation are identical to the enzymes that bring about the metabolic conversion
known as glycolysis. Alcoholic fermentation is a process that was known to antiquity.
5.1 Ethanol fermentation

Ethyl alcohol is produced biologically by the well-known yeast fermentation. Alcohol-
tolerant strains of Saccharomyces cerevisiae are usually used. S. cerevisiae converts
hexose sugars to ethanol and carbon dioxide, theoretically yielding 5 1 and 49 percent by
weight, respectively. S. anamensis and Schizosaccharomyces pombe are also used.
Candida pseudotropicalis is utilized for the ethanol fermentation from lactose, and C.
utilis from pentoses. Ethanol can be fermented from any carbohydrate, although starchy
or cellulosic materials require a pre treatment step for hydrolysis. The usable raw
materials can be categorized as saccharin (sugarcane, sugar beets, molasses, and fruit
juices), starchy (cereals and potatoes), or cellulosic (wood and waste sulfite liquor). The
environmental conditions of the alcoholic fermentation vary somewhat, depending
primarily on the strain of yeast. Acidic conditions are used to inhibit bacterial
contaminants. The initial pH is in the range of 4.0 to 5.5. Suitable temperatures are of the
order of 20 to 30 deg C. Industrial alcoholic fermentations are normally operated on a
batch basis, the process being completed within 50 hours. Yields are in excess of 90
percent of theoretical, based on fermentable sugars. The concentration of alcohol in the

276

Biochemical Energy Conversion Processes

culture medium depends on the alcohol tolerance of the yeast. Typically, this is on the
order of 10 to 20 percent which is increased by distillation and other techniques. The
economics of the ethanol fermentation depend on the cost associated with the
carbohydrate feed material and the market for nonalcoholic by-products. These by-
products consist of grain residues, recovered carbon dioxide, and the residual cells.
Recovered grain and cells are normally sold as feed materials.

Table 2. Heats of combustion and costs of various fuels

Fuel

kcal/gram*

Btu/pound

$/million
Btu

Ethanol

327.6

12,790

Synthetic

6.54-10.70

Fermentative

17.82-23.80

Hydrogen

68.4

61,500

0.89-1.02

Methane

210.8

23,600

Natural gas — wellhead

0.20-0.25

Consumers

0.75-1.00

Anaerobic digestion

Substitute natural gas

0.52-1.50

Methanol

170.9

9,990

Natural

14.68

Synthetic

3.86

Isopropanol

474.8

14,210

Synthetic

5.18

In recent years, chemosynthesis has largely displaced fermentation for the industrial
production of ethyl alcohol. Synthetic ethanol is manufactured from ethylene by

An Introduction to Energy Sources 277

absorption in concentrated sulfuric acid followed by hydrolysis of the ethyl sulfates to
ethyl alcohol, or by the direct catalytic hydration of ethylene.

As of the mid-1970s, 80 percent of the ethanol synthesized in the United States is via the
catalytic process (ref. 10). The synthetic processes yield 0.25 gallon ethanol per pound of
ethylene and 0.58 gallon per gallon of ethyl sulfate. Mid-1970s prices for industrial ethyl
alcohol are summarized in Table 2. Goldstein has estimated that for corn at $1.80 per
bushel (1974 support price was $1.30 per bushel* (8 corn/dry gallon)), fermentation is
competitive when ethylene exceeds $0.18 per pound, approximately triple the 1974 price.
* 1 US bushel = The United States or Winchester bushel was originally defined as the
volume of a cylindrical container 18 1% inches in diameter and 8 inches deep; it is now
defined as 2150.42 cubic inches exactly.
1 US bushel = 35.24 liters = 8 corn/dry gallon

5.2 Butanol-isopropanol fermentation

The butanol-isopropanol fermentation is mediated by the anaerobic bacterium
Clostridium butylicum. A wide variety of carbohydrate feeds may be used. Saccharin
feeds yield 30 to 33 percent mixed solvents, based on the original sugars. At 33 to 37 deg
C. the fermentation is complete within 30 to 40 hours. Product ratios vary with the strain
and with culture conditions, but are normally in the range 33 to 65 percent n-butanol, 19
to 44 percent isopropanol, 1 to 24 percent acetone, and to 3 percent ethanol. This
fermentation has been supplanted by petrochemical synthetic processes.

5.3 Methane fermentation

Methane and carbon dioxide are the primary gaseous end products of the anaerobic
digestion process which have been widely used for many years in the stabilization of
organic sewage solids. The quality of the digester off-gases is dependent upon feed
composition. Mixed feeds normally yield approximately 65 percent methane and 35
percent carbon dioxide. Approximately equal volumes arise from carbohydrates, and the
methane yield increases with proteins and lipids. In addition, the product gases contain
small volumes of hydrogen sulfide and nitrogen. The generation of methane occurs as the
last step of a series of biochemical reactions. The reactions are divided into three groups,
each mediated by heterogeneous assemblages of microorganisms, primarily bacteria. A
complex feed, consisting of high-molecular-weight bipolymers, such as carbohydrates,

278 Biochemical Energy Conversion Processes

fats, and proteins, undergoes exocellular enzymatic hydrolysis as the first step. The
hydrolytic end products are the respective monomers (or other low-molecular-weight
residues), such as sugars, fatty acids, and amino acids. These low-molecular-weight
residues are taken up by the bacterial cell before further metabolic digestion. The second
step is acid production in which the products of hydrolysis are metabolized to various
volatile organic fatty acids. The predominant fatty acids are acetic and propionic acids.
Other low-molecular-weight acids, such as formic, butyric and valeric acid have been
observed. Additional end products of the acid production step include lower alcohols and
aldehydes, ammonia, hydrogen sulfide, hydrogen, and carbon dioxide.
The products of the acid generation step are metabolized by the methane-producing
bacteria to yield carbon dioxide and methane, and, in addition, methane arises from
metabolic reactions involving hydrogen and carbon dioxide. Anaerobic digestion of
organic solid wastes has been investigated as an alternative methane source. Various cost
estimates have been made which indicate production costs, including gas purification and
compression, in the range of $0.40 to $2.00 per million Btu. The major cost items, and
sources of variability in the estimates, are the digester capital costs, waste sludge disposal
cost, and the credit or debit associated with the collection and preparation of the solid
waste feed material. Multiple staging and separate optimization of anaerobic digestion
may provide reduced capital costs through lower detention times and reduced operation
and maintenance costs by improved process stability.
5.4 Hydrogen fermentation

Hydrogen gas is a product of the mixed acid fermentation of Escherichia coli, the
butylene glycol fermentation of Aerobacter, and the butyric acid fermentations of
Clostridium spp. A possible fruitful research approach would be to seek methods of
improving the yield of hydrogen.
6. Biochemical fuel cells

Young et al. have discussed the possibilities of utilizing biological processes as an
integral part of fuel cells. They define three basic types of biochemical fuel cells: (1)
depolarization cells in which the biological system removes an electrochemical product,
such as oxygen; (2) product cells in which an electrochemically active reactant, such as
hydrogen, is biologically produced; and (3) redox cells (oxidation-reduction) in which

An Introduction to Energy Sources

279

electrochemical products are converted to reactants (ferricyanide/ferrocyanide system) by
the biological system. Young et al. concluded that application of biochemical fuel cells
will most probably involve immobilized enzymes as a method of increasing efficiency
and decreasing costs.

During the 20th century, energy consumption increased dramatically and an unbalanced
energy management exists. While there is no sign that this growth in demand will abate
(particularly amongst the developing nations), there is now an awareness of the
transience of nonrenewable resources and the irreversible damage caused to the
environment. In addition, there is a trend towards the miniaturization and portability of
computing and communications devices. These energy-demanding applications require
small, light power sources that are able to sustain operation overlong periods of time,
particularly in remote locations such as space and exploration.

anode

growth
medium

Shodoferax

fertireditcens

bacterium

anaerobic conditions

porous membrane

aerobic conditions

Fig. 4. A biofuel cell using R. ferrireducens

Biofuel cells use biocatalysts for the conversion of chemical energy to electrical energy
As most organic substrates undergo combustion with the evolution of energy, the
biocatalyzed oxidation of organic substances by oxygen or other oxidizers at two-
electrode interfaces provides a means for the conversion of chemical to electrical energy.

280 Biochemical Energy Conversion Processes

Abundant organic raw materials such as methanol, organic acids, or glucose can be used
as substrates for the oxidation process, and molecular oxygen or H2O2 can act as the
substrate being reduced. The extractable power of a fuel cell (Pcell) is the product of the
cell voltage (Vcell) and the cell current.
7. Biological H 2 production

The inevitable consumption of all our supplies of fossil fuels requires the development of
alternative sources of energy for the future. Introduction of a hydrogen economy will gain
great importance due to the promise of using hydrogen over fossil fuels. These
advantages include its limitless abundance and also its ability to burn without generating
any toxic byproducts, where the only by-product of hydrogen combustion is water. Steam
reforming is the major process for the production of hydrogen presently. This process has
several disadvantages. For example, it is a thermally inefficient process (about 90 %
including the convection zone) and there are mechanical and maintenance issues. The
process is difficult to control and reforming plants require a large capital investment.
Hence to meet the increasing demand for this future fuel, alternatives to reforming
processes are essential. Direct photo-biological H 2 production by photosynthetic
microorganisms is an active developing field nowadays. Realization of technical
processes for large-scale photo-biological H 2 production from water, using solar energy,
would result in a major novel source of sustainable, environmentally friendly and
renewable energy. The unique biological process of photosynthesis in which solar energy
is used to split water is combined with the natural capacity to combine obtained products
into H 2 , catalyzed by enzymes called hydrogenases. In nature, only cyanobacteria and
green algae possess water oxidizing photosynthesis and H 2 production, providing the
option to form hydrogen from sun and water. Anabaena variabilis ATCC 29413 is a
filamentous heterocyst-forming cyanobacterium that fixes nitrogen and C0 2 using the
energy of sunlight via oxygen-evolving plant-type photosynthesis. In addition, this strain
has been studied extensively for the production of hydrogen using solar energy. It has a
complex life cycle that includes multiple types of differentiated cells: heterocysts for
nitrogen fixation, akinetes (spores) for survival, and hormogonia for motility and for the
establishment of symbiotic associations with plants and fungi. Biomass-derived synthesis
gas can provide a renewable route to hydrogen. A novel bacterial process has been

An Introduction to Energy Sources 281

proposed as an alternative to the conventional high-temperature catalytic process for the
production of H2 from synthesis gas via the Water-Gas Shift (WGS) reaction. Hydrogen
can be produced via pyrolysis or gasification of biomass resources such as agricultural
residues like peanut shells; consumer wastes including plastics and waste grease; or
biomass specifically grown for energy uses. Biomass pyrolysis produces a liquid product
(bio-oil) that contains a wide spectrum of components that can be separated into valuable
chemicals and fuels, including hydrogen. Increase in the production of hydrogen from
biomass-derived glucose and attainment of the maximum molar yield of H2, can be
achieved through the enzymes of the pentose phosphate cycle in conjunction with a
hyperthermophilic hydrogenase. This process centers on three NADP+ dependent
enzymes, glucose-6 phosphate dehydrogenase (G6PDH), 6-phosphogluconate
dehydrogenase (6PGDH) and hydrogenase from Pyrococcus furiosus. The
dehydrogenases are currently obtained from mesophilic sources.

H 2 +

Hydrogenase Hydrogenase

NADP NADPH NADP NADPH

Glucose-6- ■ -f- 6-Phosphgluconic ■ ♦ Ribulose-5

Phosphate V# ^ acid (6-PG) \^ ^ phosphate

[G-6-P) ^C0 2 (Ru-5-P)

Fig. 5. In vitro enzymatic pathway to produce molecular hydrogen

The enzymatic conversion of cellulosic waste to H 2 via an in vitro enzymatic pathway
involves the conversion of potential glucose sources such as cellulose by cellulases and
plant sap (i.e. sucrose) by invertase and glucose isomerase to glucose. Glucose, the sugar
produced by photosynthesis, is also renewable, unlike fossil fuels such as oil. The glucose
substrate is then oxidized and the cofactor, NADP+ is simultaneously reduced. The
presence of a pyridine dependent- hydrogenase in this system causes the regeneration and
recycling of NAD(P)+ with the concomitant production of molecular hydrogen. The
overall aim is to increase the production of hydrogen from biomass-derived glucose and
achieve the maximum molar yield of H 2 by employing the enzymes of the pentose
phosphate pathway in conjunction with the hydrogenase from Pyrococcus furiosus. This

282 Biochemical Energy Conversion Processes

will also require the future development of an immobilized enzyme bioreactor for
efficient hydrogen production at high theoretical yields. If this could be achieved
practically, this would represent a major innovation that would advance our abilities to
develop an efficient and practical system for biohydrogen production. The main
advantage over hydrogen production by fermentation is that close-to-theoretical yields of
hydrogen from sugar would be possible.
8. Bio diesel

Transesterification of a vegetable oil was conducted as early as 1853, by scientists E.
Duffy and J. Patrick, many years before the first diesel engine became functional. Rudolf
Diesel's prime model, a single 10 ft (3 m) iron cylinder with a flywheel at its base, ran on
its own power for the first time in Augsburg, Germany on August 10, 1893. In
remembrance of this event, August 10 has been declared International Biodiesel Day.
Diesel later demonstrated his engine and received the "Grand Prix" (highest prize) at the
World Fair in Paris, France in 1900. This engine stood as an example of Diesel's vision
because it was powered by peanut oil a biofuel, though not strictly biodiesel, since it was
not transesterified. He believed that the utilization of a biomass fuel was the real future of
his engine. In a 1912 speech, Rudolf Diesel said, "the use of vegetable oils for engine
fuels may seem insignificant today, but such oils may become, in the course of time, as
important as petroleum and the coal-tar products of the present time". Biodiesel is a clear
amber-yellow liquid with a viscosity similar to petrodiesel, the industry term for diesel
produced from petroleum. It can be used as an additive in formulations of diesel to
increase the lubricity of pure ultra-low sulfur petrodiesel (ULSD) fuel. Much of the world
uses a system known as the "B" factor to state the amount of biodiesel in any fuel mix, in
contrast to the "BA" system used for bioalcohol mixes. For example, fuel containing 20
% biodiesel is labeled B20. Pure biodiesel is referred to as B100. The common
international standard for biodiesel is EN 14214. Biodiesel refers to any diesel-equivalent
biofuel usually made from vegetable oils or animal fats. Several different kinds of fuels
are called biodiesel: usually biodiesel refers to an ester, or an oxygenate, made from the
oil and methanol, but alkane (non-oxygenate) biodiesel, that is, biomass-to-liquid (BTL)
fuel is also available. Sometimes even unrefined vegetable oil is called "biodiesel".
Unrefined vegetable oil requires a special engine, and the quality of petrochemical diesel

An Introduction to Energy Sources

283

is higher. In contrast, alkane biodiesel is of a higher quality than petrochemical diesel,
and is actually added to petro-diesel to improve its quality.

Biodiesel has physical properties very similar to petroleum-derived diesel fuel, but its
emission properties are superior. Using biodiesel in a conventional diesel engine
substantially reduces emissions of unburned hydrocarbons, carbon monoxide, sulfates,
polycyclic aromatic hydrocarbons, nitrated polycyclic aromatic hydrocarbons, and
particulate matter. Diesel blends containing up to 20% biodiesel can be used in nearly all
diesel-powered equipments, and higher-level blends and pure biodiesel can be used in
many engines with little or no modification. Lower-level blends are compatible with most
storage and distribution equipments, but special handling is required for higher-level
blends.

Biodiesels are biodegradable and non-toxic, and have significantly fewer emissions than
petroleum-based diesel (petro-diesel) when burnt. Biodiesel functions in current diesel
engines, and is a possible candidate to replace fossil fuels as the world's primary transport
energy source. With a flash point of 160 °C, biodiesel is classified as a non-flammable
liquid by the Occupational Safety and Health Administration. This property makes a
vehicle fueled by pure biodiesel far safer in an accident than one powered by petroleum
diesel or the explosively combustible gasoline. Precautions should be taken in very cold
climates, where biodiesel may gel at higher temperatures than petroleum diesel.

Glycerine

Biodeisd

Glycerols

Fig. 6. Schematic setup for biodiesel production

284 Biochemical Energy Conversion Processes

Biodiesel can be distributed using today's infrastructure, and its use and production is
increasing rapidly (especially in Europe, the United States, and Asia). Fuel stations are
beginning to make biodiesel available to consumers, and a growing number of transport
fleets use it as an additive in their fuel. Biodiesel is generally more expensive to purchase
than petroleum diesel, although this differential may diminish due to economies of scale,
the rising cost of petroleum, and government subsidization favoring the use of biodiesel.
8.1 Two real-world issues involving the use of biodiesel

There are a number of different feed stocks (methyl esters, refined canola oil, french fry
oil, etc.) that are used to produce biodiesel. But in the end they all have a few common
problems. First, any of the biodiesel products have a problem of gelling when the
temperatures get below 40 °F. At the present time there is no available product that will
significantly lower the gel point of straight biodiesel. A number of studies have
concluded that winter operations require a blend of bio, low sulfur diesel fuel (LS), and
kerosene (K). The exact blend depends on the operating environment. We have seen
successful operations running 65% LS, 30% K, and 5% bio. Other areas have run 70%
LS , 20% K, and 10% bio. We have even seen 80% K, and 20% bio. Which mixture you
choose is based on volume, component availability, and local economics.
The second problem with biodiesel is that it has a great affinity for water. Some of the
water is residual to the processing, and some is coming from storage tank condensation.
The presence of water is a problem for a number of reasons: Water reduces the heat of
combustion. This means more smoke, harder starting, less power. Water will cause
corrosion of vital fuel system components fuel pumps, injector pumps, fuel lines, etc.
Water, as it approaches 32°F begins to form ice crystals. These crystals provide sites of
nucleation and accelerate the gelling of the residual fuel. Water is part of the respiration
system of most microbes. Biodiesel is a great food for microbes and water is necessary
for microbe respiration. The presence of water accelerates the growth of microbe colonies
which can seriously plug up a fuel system. Bio users that have heated fuel tanks face a
year round microbe problem.
9. Biogas

Biogas, also called digester gas, typically refers to methane produced by the fermentation
of organic matter including manure, wastewater sludge, municipal solid waste, or any

An Introduction to Energy Sources 285

other biodegradable feedstock, under anaerobic conditions. Biogas is also called swamp
gas and marsh gas, depending on where it is produced. The process is popular for treating
many types of organic waste because it provides a convenient way of turning waste into
electricity, decreasing the amount of waste to be disposed of, and of destroying disease
causing pathogens which can exist in the waste stream. The use of biogas is encouraged
in waste management because it does not increase the amount of carbon dioxide in the
atmosphere, which is responsible for much of the greenhouse effect, if the biomass it is
fueled on is regrown. Also, methane burns relatively cleanly compared to coal.
Processing of the biodegradable feedstock occurs in an anaerobic digester, which must be
strong enough to withstand the buildup of pressure and must provide anaerobic
conditions for the bacteria inside. Digesters are usually built near the source of the
feedstock, and several are often used together to provide a continuous gas supply.
Products put into the digester are composed mainly of carbohydrates with some lipids
and proteins.

More recently, developed countries have been making increasing use of gas generated
from both wastewater and landfill sites. Landfill gas production is incidental and usually
nothing is done to increase gas production or quality. There are indications that slightly
wetting the waste with water when it is deposited may increase production, but there is a
concern that gas production would be large at first and then drop sharply. Even if not
used to generate heat or electricity, landfill gas must be disposed of or cleaned because it
contains trace volatile organic compounds (VOCs), many of which are known to be
precursors to photochemical smog. Because landfill gas contains these trace compounds,
the United States Clean Air Act, and Part 40 of the Federal Code of Regulations, requires
landfill owners to estimate the quantity of VOCs emitted. If the estimated VOC emissions
exceed 50 metric tons, then the landfill owner is required to collect the landfill gas, and
treat it to remove the entrained VOCs. Usually, treatment is by combustion of the landfill
gas. Because of the remoteness of landfill sites, it is sometimes not economically feasible
to produce electricity from the gas.

Biogas digesters take the biodegradable feedstock, and convert it into two useful
products: gas and digestate. The biogas can vary in composition typically from 50-80%
methane, with the majority of the balance being made up of carbon dioxide. The digestate

286

Biochemical Energy Conversion Processes

comprises of lignin and cellulose fibers, along with the remnants of the anaerobic
microorganisms. This digestate can be used on land as a soil amendment, to increase
moisture retention in soil and improve fertility.

Inlet tank

Gas outlet pipe
Gas holder

Slurry level

On tk I pit

<; :

ten Ira]
£uide pipe

Digester

Floting dome type bio gas digester

hi .

Inlet tank
Gas valve

Hydraulic
duiiik'i

Ground
level

Outlet
pit

Outlet passage

Fixed dome type bio gas digester

Fig. 7. Two different types of biogas digesters

If biogas is cleaned up sufficiently, biogas has the same characteristics as natural gas.
More frequently, it is burnt with less extensive treatment on site or nearby. If it is burnt
nearby, a new pipeline can be built to carry the gas there. If it is to be transported long
distances, laying a pipeline is probably not economical. It can be carried on a pipeline
that also carries natural gas, but it must be very clean to reach pipeline quality.
10. Conclusion

Widespread application of biochemical processes will be a function of competition which
can occur at any of three levels. At the first level is competition for raw materials. Strong
pressure will exist for utilization of photosynthate for food and feed. Waste materials also
face competition for alternative uses. Demand may force decisions to direct fermentation
toward food and feed production instead of fuel generation. The third level of
competition is alternative uses of the end product, such as synthetic feedstock and
solvents. The biologically derived products will complement the existing energy
structure. Methane gas is easily transportable in the well-developed natural gas

An Introduction to Energy Sources 287

distribution system. Ethyl and isopropyl alcohols have been utilized as gasoline additives
for internal combustion engines. Widespread utilization of hydrogen fuel has been
anticipated. It is apparent that the production of fuels by biochemical means is feasible
and desirable. Process economics and efficiencies require improvement which, in turn,
necessitates a concerted and coordinated research effort on the part of the biologists and
the engineers. Enzyme and genetic engineering hold the key to improved process
efficiencies.
References

1. Rabinowitch, E., and Govindjee: "Photosynthesis," Wiley, New York, 1969.

2. Odum, E.P. "Fundamentals of Ecology," Saunders, Philadelphia, 1959.

3. Prochazka, G.J., W.J. Payne, and W.R. Mayberry: Calorific Contents of
Microorganisms, Biotech. andBioeng. 15, 1007-1010 (1973).

4. Oswald, W.J., and C.G. Golueke: Biological Transformation of Solar Energy,
Advan. Appl. Microbiol, 2, 223-262 (1960).

5. Hollaender, A.K., J. Monty, R.M Pearlstein, F. Schmidt-Bleek, W.T. Snyder, and
E. Volkin: "An Inquiry into Biological Energy Conversion," University of

Tennessee, Knoxville, Tenn., 1972.

6. Aiba, S., A.E. Humphrey, andN.F. Millis: "Biochemical Engineering," 2 n ed.,
Academic, New York, 1973.

7. Prescott S.C., and C.G. Dunn: "Industrial Microbiology," McGraw-Hill, New York,
1959.

8. Narinder I. Heyer and Jonathan Woodward, Proceedings of the 2001 DOE Hydrogen
Program Review, NREL/CP-570-30535.

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